Photocurable resin composition and a method for producing the same

• US 6,075,065 A
• Filed: 12/04/1997
• Issued: 06/13/2000
• Est. Priority Date: 12/20/1996
• Status: Expired due to Fees

• Current Assignee: Mitsui Chemicals Incorporated (Mitsui Chemicals), Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited, Takeda Chemical Industries, Ltd. (Takeda Pharmaceutical Company Limited)
• Inventors: Yamamoto, Akira, Nishimura, Mitsuhiro, Uemura, Takashi, Asano, Masatoshi, Kozakai, Shouhei, Yamazaki, Kyuya
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): McClendon, Sanza L.
• Application Number:
  US08/985,630
• Time in Patent Office: 922 Days
• Field of Search: 522/96, 522/64, 522/28, 522/93, 522/90
• US Class Current: 522/64
• CPC Class Codes: C03C 25/106 Single coatings
• CPC Class Codes: C08F 290/067 Polyurethanes; Polyureas
• CPC Class Codes: C08K 5/5397 Phosphine oxides
• CPC Class Codes: C08L 75/14 Polyurethanes having carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09J 4/06 Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

Abstract

The invention provides a photocurable resin composition which inhibits the deactivation of a bisacylphosphine oxide-series photopolymerization initiator and is useful for coating optical fibers. The photocurable resin composition comprises (A) a polyurethane (meth)acrylate oligomer, (B) an ethylenically unsaturated compound, (C) a bisacylphosphine oxide-series photopolymerization initiator, and (D) a tertiary amine and no tin component. Incorporation of the component (D) inhibits the decomposition and deactivation of the component (C). The component (A) may contain an aliphatic C_14-40 polyol (hydrogenated dimerdiol, 12-hydroxystearyl alcohol) as a polyol component. This resin composition is used for a primary coating of a glass fiber or an indirect coating of an optical fiber through the primary layer, the coating layer being cured by light irradiation to provide an optical fiber coated with the resin composition.

Claims

1. A photocurable resin composition which comprises (A) a urethane (meth)acrylate oligomer containing a C_14-40 polyol unit as a polyol component, (B) an ethylenically unsaturated compound, (C) a bisacylphosphine oxide-series photopolymerization initiator shown by the following formula (i), ##STR4## wherein R₁ represents a straight or branched C_1-12 alkyl group, a cycloalkyl group, or an aryl group which may be substituted with a straight or branched C_1-12 alkyl group or a halogen atom;

R₂ and R₃ independently represent a hydrogen atom, a straight or branched C_1-12 alkyl group, or a straight or branched C_1-12 alkoxy group; and

R₄ and R₅ independently represent a hydrogen atom or a straight or branched C_1-12 alkyl group, and (D) a tertiary amine as a urethanating catalyst, said photocurable resin composition having substantially no tin component and being substantially free from a tin-series catalyst to prevent the deactivation of the bisacylphosphine oxide-series photopolymerization initiator.

2. The photocurable resin composition as claimed in claim 1, wherein R₁ is a branched C_6-12 alkyl group, a C_5-10 cycloalkyl group, or an aryl group which may be substituted with a straight or branched C_1-4 alkyl group;

R₂ and R₃ independently represent a hydrogen atom, a straight or branched C_1-4 alkyl group or a straight or branched C_1-4 alkoxy group; and

R₄ and R₅ independently represent a hydrogen atom or a straight or branched C_1-4 alkyl group.

3. The photocurable resin composition as claimed in claim 1, wherein R₁ is a branched C_6-12 alkyl group;

each of R₂ and R₃ is a C_1-2 alkyl group or a C_1-2 alkoxy group; and

each of R₄ and R₅ is a methyl group.

4. The photocurable resin composition as claimed in claim 1, wherein the proportion of the bisacylphosphine oxide-series photopolymerization initiator relative to the tertiary amine is such that the former/the latter is in the range of 100/0.1 to 100/10 (by weight).

5. The photocurable resin composition as claimed in claim 4, wherein said C_14-40 polyol unit is an aliphatic diol derived from a higher fatty acid.

6. The photocurable resin composition as claimed in claim 5, wherein said C_14-40 polyol unit is at least one member selected from the group consisting of a hydrogenated dimerdiol and 12-hydroxystearyl alcohol.

7. The photocurable resin composition as claimed in claim 1, wherein said urethane (meth)acrylate oligomer (A) is:

(A1) a polyurethane (meth)acrylate oligomer whose polyol component comprises an aliphatic C_14-40 polyol,

(A2) a polyurethane (meth)acrylate oligomer whose polyol component comprises a mixture of the aliphatic C_14-40 polyol and at least one member selected from the group consisting of polyether polyols, polyester polyols, and polycarbonate polyols, or

(A3) a mixture of the polyurethane (meth)acrylate oligomer (A1), and a polyurethane (meth)acrylate oligomer whose polyol component comprises at least one member selected from the group consisting of polyether polyols, polyester polyols, and polycarbonate polyols.

8. The photocurable resin composition as claimed in claim 5, wherein the proportion of the C_14-40 polyol unit is 1 to 50% by weight based on the total amount of the polyurethane (meth)acrylate oligomer.

9. The photocurable resin composition as claimed in claim 1, which is used for the coating of an optical fiber.

10. A method for producing a photocurable resin composition containing (D) a tertiary amine as a urethanating catalyst, which method comprises mixing (A) a urethane (meth)acrylate oligomer containing a C_14-40 polyol unit as a polyol component, (B) an ethylenically unsaturated compound, and (C) the bisacylphosphine oxide-series photopolymerization initiator of claim 1, said photocurable resin composition having substantially no tin component and being substantially free from a tin-series catalyst to prevent the deactivation of the bisacylphosphine oxide-series photopolvmerization initiator.

11. A method for coating an optical fiber which comprises the steps of coating a glass fiber directly or indirectly with the photocurable resin composition of claim 1, and curing the resin composition by light irradiation.

12. A photocurable resin composition which comprises (A) a urethane (meth)acrylate oligomer containing a unit of a copolymer of an alkylene oxide and an aliphatic C_14-40 polyol, (B) an ethylenically unsaturated compound, (C) the bisacylphosphine oxide-series photopolymerization initiator of claim 1, and (D) a tertiary amine as a urethanating catalyst, said photocurable resin composition having no tin component and being substantially free from a tin-series catalyst to prevent the deactivation of the bisacylphosphine oxide-series photopolymerization initiator.

13. A photocurable resin composition as claimed in claim 12, wherein the urethane (meth)acrylate oligomer (A) is an oligomer containing a unit of a copolymer of a C_2-4 alkylene oxide and an aliphatic C_14-40 polyol.