Process for preparing a laminate of metal and a polyolefin resin

• US 5,275,848 A
• Filed: 10/02/1991
• Issued: 01/04/1994
• Est. Priority Date: 10/02/1990
• Status: Expired due to Fees

• Current Assignee: Mitsui Chemicals Incorporated (Mitsui Chemicals)
• Original Assignee: Mitsui Petrochemical Industries, Ltd.
• Inventors: Saito, Tatsuo, Mito, Kazunori, Ishimaru, Naoshi
• Primary Examiner(s): Beck, Shrive
• Assistant Examiner(s): DUDASH, DIANA L
• Application Number:
  US07/769,818
• Time in Patent Office: 825 Days
• Field of Search: 427/409, 427/185, 427/377, 427/379, 427/435, 427/333, 427/412.3
• US Class Current: 427/409
• CPC Class Codes: B05D 1/24 Applying particulate materials
• CPC Class Codes: B05D 2202/00 Metallic substrate
• CPC Class Codes: B05D 2507/00 Polyolefins
• CPC Class Codes: B05D 3/0254 After-treatment
• CPC Class Codes: B05D 3/102 Pretreatment of metallic substrates C23C takes precedence
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C

Abstract

A process for preparing a laminate by coating the surfaces of a metal substrate that has been treated with an anchor coating agent, with a modified olefin type resin and heat-adhering the olefin resin onto the surfaces of the metal substrate. The process of this invention is characterized by applying heat-treatment to the laminate at the time of adhesion or after the adhesion in the presence of a treating agent which consists of a compound prescribed in the general formulae (1) and (2). ##STR1## The laminate prepared by this process withstands deterioration of adhesion caused by aging, particularly in an atmosphere where water is present.

Claims

1. In a process for preparing a laminate of a metal substrate and a modified polyolefin, wherein said modified polyolefin comprises a homopolymer of an olefin or a copolymer of olefins grafted with an unsaturated carboxylic acid or an anhydride thereof in an amount of 0.001 to 3% by weight, based on the weight of the polyolefin, the improvement comprising the steps of:

coating the modified polyolefin onto a surface of the metal substrate that has been coated with an anchor coating agent; and

heating-adhering the modified polyolefin onto said surface of the metal substrate at a temperature higher than the melting point of the modified polyolefin to obtain a laminate;

wherein the obtained laminate is heat-treated at a temperature of from 150°

to 300°

C. in contact with a treating agent which is at least one compound selected from the group consisting of

a compound of the formula (1);

space="preserve" listing-type="equation">R.sup.1 --Y--R.sup.2 (

     1)

wherein R¹ is a substituted or unsubstituted monovalent hydrocarbon group, Y is an oxygen atom, a sulfur atom or a group>

NR², and R² is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and

a compound of the formula (2);

##STR4## wherein R³ is a substituted or unsubstituted monovalent hydrocarbon group, and Z is an oxygen atom, a sulfur atom, or a group represented by the formula (3);

space="preserve" listing-type="equation">═

N--R.sup.9 (

     3)

wherein R⁹ is a hydrogen atom or a substituted or

unsubstituted monovalent hydrocarbon group, and R⁴ is a hydrogen atom, an amino group, a substituted or unsubstituted monovalent hydrocarbon group, or a group represented by the formula (4);

space="preserve" listing-type="equation">--OR.sup.5 (

     4)

wherein R⁵ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, or

a group represented by the formula (5);

##STR5## wherein R⁶ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and wherein the group Z is a sulfur atom, R⁴ is a substituted or unsubstituted monovalent hydrocarbon group, and

when the group Z is the group of the formula (3), R⁴ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and

when R⁴ is the group of the formula (5) and Z is the oxygen atom, the group R³ and the group R⁶ coupled together may form a substituted or unsubstituted divalent hydrocarbon group;

or

said heat-adhesion is carried out using the modified polyolefin containing the treating agent.

2. A process according to claim 1,

wherein the treating agent is contained in the modified polyolefin in an amount of 1 to 10,000 ppm.

3. A process according to claim 1,

wherein the compound used as the treating agent is an oxygen-containing organic compound.

4. A process according to claim 3,

wherein said oxygen-containing organic compound is an alcohol having a valence of 1 to 3.

5. A process according to claim 4,

wherein said alcohol is an ethylene glycol.

6. A process according to claim 1,

wherein a base polymer of said modified polyolefin is a homopolymer or a copolymer of α

-olefin.

7. A process according to claim 3,

wherein said heat-treatment of the obtained laminate is carried out in an atmosphere that contains the oxygen-containing organic compound.