Active energy ray-curable resin composition

• US 4,839,400 A
• Filed: 03/06/1987
• Issued: 06/13/1989
• Est. Priority Date: 03/10/1986
• Status: Expired due to Term

• Current Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Original Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Inventors: Sato, Yasufumi, Noguchi, Hiromichi, Munakata, Megumi
• Primary Examiner(s): Bleutge, John C.
• Assistant Examiner(s): BUTTNER, DAVID J
• Application Number:
  US07/022,930
• Time in Patent Office: 830 Days
• Field of Search: 525/289, 525/290, 525/910, 525/913, 525/279, 522/92, 522/102, 522/14, 522/36, 522/43, 522/46, 522/48, 522/63, 522/33, 522/69, 522/68, 522/77, 522/121, 522/106, 522/95, 156/273.3, 346/140 R
• US Class Current: 522/14
• CPC Class Codes: C08F 285/00 Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• CPC Class Codes: C08F 290/04 Polymers provided for in subclasses C08C or C08F
• CPC Class Codes: G03F 7/032 with binders

Abstract

An active energy ray-curable resin composition comprises (A) a graft copolymerized polymer comprising graft chains composed mainly of structural units derived from at least one monomer selected from the group consisting of (a) hydroxyl containing (meth)acrylic monomers, (b) amino or alkylamino containing (meth)acrylic monomers, (c) carboxyl containing (meth)acrylic or vinyl monomers, (d) N-vinylpyrrolidone, (e) vinylpyridine or its derivatives and (f) (meth)acrylic amide derivatives represented by the general formula (II) shown below: ##STR1## (wherein R₁ is hydrogen or methyl group and R₂ is hydrogen or an alkyl or acyl group having 1 to 4 carbon atoms which may have hydroxyl group added to trunk chains composed mainly of structural units compsiting at least one monomer selected from the group consisting of the monomer represented by the general formula (I) shown below: ##STR2## (wherein R₁ to R₈ each represent hydrogen or methyl group), alkyl (meth)acrylates, acrylonitrile and styrene, and (B) a monomer having an ethylenically unsaturated bond.

Claims

1. An active energy ray-curable resin composition comprising:

(A) a graft copolymerized polymer comprising graft chains composed mainly of structural units derived from at least one monomer selected from the group consisting of (a) hydroxyl containing (meth)acrylic monomers, (b) amino or alkylamino containing (meth)acrylic monomers, (c) carboxyl containing (meth)acrylic or vinyl monomers, (d) N-vinylpyrrolidone, (e) vinylpyridine or its derivatives and (f) (meth)acrylic amide derivatives represented by the general formula (II) shown below;

##STR7## wherein R₁ is hydrogen or methyl group and R₂ is hydrogen or an alkyl or acryl group having 1 to 4 carbon atoms which may have a hydroxyl group, added to trunk chains comprising both structural units formed from at least one monomer represented by the general formula (I) shown below;

##STR8## wherein R₁ to R₈ each represent hydrogen or methyl group, and structural units formed from at least one monomer selected from the group consisting of alkyl (meth)acrylates, acrylonitrile and styrene, and (B) a monomer having an ethylenically unsaturated bond.

2. An active energy ray-curable resin composition according to claim 1, containing 20 to 80 parts by weight of the graft copolymerized polymer (A) and 80 to 20 parts by weight of the monomer having an ethylenically unsaturated bond (B).

3. An active energy ray-curable resin composition according to claim 1, wherein the proportion of the monomer represented by the formula (I) formulated in the graft copolymerized polymer (A) is within the range of from 1 to 30% by weight.

4. An active energy ray-curable resin composition according to claim 1, wherein said monomer having an ethylenically unsaturated bond has a boiling point of 100°

C. or higher under the atmospheric pressure and at least two ethylenically unsaturated bonds.

5. An active energy ray-curable resin composition according to claim 1, wherein said monomer having an ethylenically unsaturated bond is selected from the group consisting of (i) (meth)acrylic acid esters of polyfunctional epoxy resins having two or more epoxy groups in one molecule;

(ii) (meth)acrylic acid esters of alkyleneoxide addition products of polyhydric alcohols;

(iii) polyester (meth)acrylates having (meth)acrylic acid ester group at the terminal ends of the molecular chains of polyesters having molecular weights of 500 3000 comprising dibasic acid and dihydric alcohol; and

(iv) the reaction products between polyisocyanates and (meth)acrylic acid monomers having hydroxyl groups.

6. An active energy ray-curable resin composition according to claim 4, further containing a monomer having only one ethylenically unsaturated bond.

7. An active energy ray-curable resin composition according to claim 1, further comprising a monomer which is subjected to ring opening by heat to be crosslinked.

8. An active energy ray-curable resin composition according to claim 7, wherein the monomer is glycidyl (meth)acrylate.

9. An active energy ray-curable resin composition according to claim 1, wherein a photopolymerizable monomer is added to some of the graft chains of said graft copolymerized polymer.

10. An active energy ray-curable resin composition according to claim 1, wherein a hydrophobic monomer is contained within the range of 0 to about 25% by weight as a component of comonomers in said graft copolymerized polymer.

11. An active energy ray-curable resin composition according to claim 1, further comprising a photopolymerization initiator.

12. An active energy ray-curable resin composition according to claim 1, further comprising 0.1 to 20 parts by weight of a photopolymerization initiator based on 100 parts by weight of the total amount of the graft copolymerized polymer (A) and the monomer having an ethylenically unsaturated bond (B).

13. An active energy ray-curable resin composition according to claim 11, wherein the photopolymerization initiator is a compound selected from the group consisting of dibenzoyl, benzoin alkyl ethers, benzophenones, anthraquinones, xanthones and acetophenones.

14. An active energy ray-curable resin composition according to claim 11, further comprising a photopolymerization accelerator.

15. An active energy ray-curable resin composition according to claim 14, wherein the photopolymerization accelerator is an amino compound.

16. An active energy ray-curable resin composition according to claim 1, further comprising an additive selected from the group consisting of catalysts for condensation cross-linking, heat polymerization inhibitors, colorants, fine particulate fillers, adhesion promotors, and plasticizers.

17. An active energy ray-curable resin composition according to claim 16, wherein the catalyst for condensation cross-linking is selected from the group consisting of sulfonic acids and carboxylic acids.

18. An active energy ray-curable resin composition according to claim 16, wherein the heat polymerization inhibitor is selected from the group consisting of hydroquinone and its derivatives, p-ethoxyphenol and phenothiazine.

19. An active energy ray-curable resin composition according to claim 16, wherein the colorant if selected from the group consisting of oil-soluble dyes and pigments.

20. An active energy ray-curable resin composition according to claim 16, wherein the fine particulate filler is selected from the group consisting of extender pigments and fine plastic particles.

21. An active energy ray-curable resin composition according to claim 16, wherein the adhesion promotor is selected from the group consisting of silane coupling agents and low molecular surfactants.

22. An active energy ray-curable resin composition according to claim 1, wherein said graft copolymer has a weight-average molecular weight of about 5000 to 300,000.