JPH03176135A - Metal laminated plate - Google Patents

Abstract

PURPOSE:To enhance initial adhesive strength, baking-resistant painting properties and durability by constituting a resin layer of a resin composition obtained by mixing a noncrystalline copolymerized polyester resin with a compound selected from a polyisocyanate compound, a polyepoxy compound and an acid anhydride and a phosphite compound. CONSTITUTION:A metal laminated plate is constituted by holding a resin layer between two metal plates and the resin layer is constituted of a resin composi tion obtained by mixing 100 pts.wt. of a noncrystalline copolymerized polyester resin, 0.5 - 20 pts.wt. of at least one kind of a compound selected from a polyisocyanate compound, a polyepoxy compound and an acid anhydride and 0.05 - 5 pts.wt. of a phosphite compound represented by formula (I), (II) or (III) (wherein R1, R1' and R1'' are a 1 - 18C hydrocarbon group or a 1 - 23C hydrocarbon group having a -COO- bond and a -CONH- bond in its molecular chain and may be same or different and m is an integer of 1 - 4).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention has high adhesive strength between metal plates, can withstand forming processes such as bending and deep drawing, and does not reduce adhesive strength due to baking due to heating during painting. This invention relates to a gold-i laminate that maintains high adhesive strength over a long period of time and has excellent durability when used at high temperatures.

[Prior Art] Metal laminates, which are made by sandwiching a resin layer between two metal plates, have been increasingly used in recent years as vibration-damping steel plates and lightweight steel plates. Particularly recently, as anti-seizure products have become coated and the environments in which they are used have become more diverse, there is a demand for anti-seizure products that have excellent paintability and durability that can withstand long-term use at high temperatures.

JP-A-84-48813 discloses a technique for using a resin composition consisting of a saturated co-fermented polyester and a polyvalent incyanate compound for such a metal laminate, and a technique for using an incyanate compound and an incyanate compound for a thermoplastic saturated polyester resin. A combination of crosslinking agents such as epoxy compounds and acid anhydrides! A technique using lt products is disclosed in Japanese Patent Laid-Open No. 64-89F385.

[Problem M to be solved by the invention] The above-mentioned JP-A-84-48813 or JP-A-84
- Metal laminates using the resin composition disclosed in Publication E19E385 as a resin layer have high adhesive strength between metal plates and can withstand forming processes such as bending and deep drawing, but baking occurs during painting. It is insufficient in adhesive strength retention and durability in long-term use at high temperatures, and its performance is not satisfactory for use in harsh environments including automobile parts.

[Means for Solving the Problems] In order to solve the above problems, the present inventors have found that the adhesive strength between metal plates is high, there is no decrease in adhesive strength during painting, and there is no decrease in adhesive strength during baking, and even after long-term use at high temperatures, the adhesive strength between metal plates is high. As a result of extensive research into metal laminates with high adhesive strength, the present invention was achieved.

That is, in the present invention, in a metal species 1 consisting of a resin layer sandwiched between two pieces of gold a Vi, the resin layer contains 100 parts by weight of an amorphous copolymerized polyester resin (A), a polyisocyanate compound, At least one compound (B) selected from polyepoxy compounds and acid anhydrides 0.5 to 2
0! and 0.0 parts of a phosphite compound (C) represented by the following general formula (I), (II) or (iff).
The present invention relates to a metal laminate comprising a resin composition obtained by mixing 0.05 to 5 parts by weight.

(However, R1, RI', and R1'' are hydrocarbon groups having 1 to 18 carbon atoms, or -COO-1-C0NH-
Represents a hydrocarbon group having a bond of 1 to 23 carbon atoms, each of which may be the same or different, m is 1 to 4
is an integer. ) A hindered phenol compound (D) represented by the following general formula 1/) is further added to the resin composition.
A gold i laminate using a resin composition to which is added in the same proportion as the phosphite compound (C) represented by the above general formula (I), (+[) or (lit), still has -
The outstanding baking properties provide excellent adhesion retention during painting and durability when used at high temperatures.

(However, R2 is an alkyl group having 1 to 18 carbon atoms, and R
2' is an alkyl group similar to R2 and may be the same as R2, R3 is a single bond, a hydrocarbon group having 1 to 18 carbon atoms, or -COO--CONH-1-〇- in the molecular chain.
A hydrocarbon group having a carbon number of 1 to 1 and having any of the μ-〇-bonds, and X is C, S
, a hydrocarbon group having 1 to 1 carbon atoms or δ Amorphous copolymerized polyester used in the present invention) M resin (
A) refers to a polyester resin that does not have a clear melting endothermic peak due to crystalline parts in p analysis by DSC, for example. Such polyesters are synthesized from glycol components and dibasic acid components. In some cases, it is also possible to copolymerize a small amount of trivalent or higher polycarboxylic acid and/or trivalent or higher polyol.

Glycol components include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5
- aliphatic glycols such as bentanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1. Alicyclic glycols such as 4-cyclohexane dimetatool, aromatic glycols such as ethylene oxide or propylene oxide adducts of bisphenol A, poly(ethylene oxide) glycol, poly(propylene oxide) glycol, poly(tetramethylene oxide) glycol, Poly (
Poly(alkylene oxide) glycols such as hexamethylene oxide) glycols, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, poly-ε-caprolactone, polyethylene adipate, polybutylene Examples include aliphatic polyester glycols such as adipate. One or more of these may be selected and used, and among these, it is preferable to use ethylene glycol and/or neopentyl glycol as an essential component.

Dibasic acid components include terephthalic acid, isophthalic acid,
Orthophthalic acid, 2. e-naphthalenedicarbone? iL
4. Aromatic dibasic acids such as 4-diphenyl dicarboxylic acid, alicyclic dibasic acids such as hydrogenated terephthalic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid,
Speric acid, azelaic acid, sebacic acid, dodecanedioic acid, brassic acid, dimer acid, and aliphatic dibasic acids can be mentioned. It is also possible to use lower alkyl esters. One or more of these are selected and used, and among these, it is preferable to use terephthalic acid and/or isophthalic acid as an essential component.

The amorphous copolymerized polyester resin (A) of the present invention is produced by combining the above-mentioned glycol and dibasic acid to form a ternary or quaternary or more copolymer by melting the glycol component and the dibasic III component. Obtained by polymerization. A preferred method is to use a dibasic acid and 1.
05 to 2.0@mol of glycol is reacted under normal pressure at a temperature of about 150 to 240° C. in the presence of a conventional esterification catalyst, or about 2.0@mol is reacted without using a catalyst.
The reaction is carried out by heating the presser at a temperature of 40 to 260°C.

When a lower alkyl ester compound of a dibasic acid is used as a starting material, the reaction is carried out under normal pressure at a temperature of about 150 to 240° C. in the presence of a conventional transesterification catalyst. Next, heating polycondensation is carried out at 220 to 290° C. under reduced pressure of 110 mmft or less, preferably 1 mmHg or less. At this time, it is preferable to use a polymerization catalyst.

Titanium compounds, tin compounds, lead compounds, etc. are used as esterification catalysts, and zinc compounds, etc. are used as transesterification catalysts.
Examples of polymerization catalysts include manganese compounds and cobalt compounds, and examples of polymerization catalysts include antimony compounds, titanium compounds, zinc compounds, and tin compounds.

The compound (B) used in the present invention is at least one compound selected from polyisocyanate compounds, polyepoxy compounds, and acid anhydrides. These compounds improve the performance of the metal laminate by reacting with the terminal functional groups of the amorphous co-adherent polyester resin and forming crosslinks.

A polyisocyanate compound is defined as having at least 2 molecules in the molecule.
A compound having at least 2.4-1 lylene diisocyanate groups, specifically 2.4-1 lylene diisocyanate+2. 6-
1-lylene cassiocyanate (commonly known as TDI), diphenylmethane diisocyanate (commonly known as MDI), polymethylene polyphenylene polyisocyanate, polyol-modified isocyanate, carposiside-modified isocyanate, hexamethylene diisocyanate (commonly known as HMDI)
, isophorone diisocyanate (commonly known as IPDI), TD
Examples include TDI adduct polyisocyanate in which I is added to trimethylolpropane or the like, polymerized polyisocyanate reacted in advance, and blocked isocyanate in which isocyanate is masked with caprolactam or the like. Among these, adduct polyisocyanates and polymerized polyisocyanates are preferred.

A polyepoxy compound is a compound having at least 62 or more epoxy groups in the molecule, and specifically includes bisphenol A-based epoxy resin, tetrabromobisphenol A-based epoxy resin, bisphenol F-based epoxy resin, and phenol. Novolac epoxy resin, tetraglycidyl metaxylene diane, tetraglycidyl-L 3
- Polyfunctional glycidyl amine compounds such as bisamine methylcyclohexane, tetraglycidyldiaminodiphenylmethane, triglycidyl-m-aminophenol, triglycidyl-p-7 minophenol, diglycidylaniline, diglyidyl orthotoluidine, l,4-butanediol Polyfunctional glycidyl ether compounds such as diglycidyl ether, l,6-hexanesiol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester ,
Examples include glycidyl ester compounds such as trimellitic acid polyglycidyl ester.

Among these, bisphenol A-based epoxy resins, diglycidyl ether compounds, and diglycidyl ester compounds are preferably used.

Examples of acid anhydrides include maleic anhydride, dodecenersuccinic anhydride, chlorendecic anhydride, sebacic anhydride polymer, phthalic anhydride, pyromellitic anhydride, cyclopenkune tetracarboxylic acid trihydrate, hexahydrophthalic anhydride,
Examples include methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, benzophenone tetracarboxylic anhydride, and the like. Among these, it is preferable to use pyromellitic anhydride and benzophenonetetracarboxylic anhydride.

At least one type of compound selected from these is used, but two or more types may be used in combination.

Compound (B) is amorphous copolymerized polyester resin (A) 1
0.00 parts by weight. 5 to 20 parts by weight is used. 0
．． If the amount is less than 5 parts by weight or more than 20 parts by weight, the initial adhesive strength will be low.

Further, a catalyst may be added to promote the reaction between these compounds and the terminal functional groups of the polyester resin. As catalysts, tertiary amines, tin compounds, etc. are used for polyisocyanate compounds, and Zn(BF+)z, 5nCl+, KOI(,3m amine, quaternary ammonium salts, imidazole compounds, etc.) are used for polyepoxy compounds. For acid anhydrides, imidacil compounds, ferric acetylacetone salts, etc. are used.

The phosphite compound (C) used in the present invention is represented by the above formula (I), (l[) or (III).

Examples of compounds represented by formula (I) include trilauryl phosphite, triisooctyl phosphite,
Trioleyl phosphite, triphenyl phosphite, triotadecyl phosphite, triisodecyl phosphite, trin-butyl phosphite,
Tris-2-ethylhexyl-phosphite, tristearyl phosphite, tris-2,4-di-tert-butylphenyl-phosphite, tris-tridecyl phosphite, tris-4-phenylphenol-phosphite, trisnonylphenyl phosphite, Examples include phenyl diisodecyl phosphite, phenyldioctyl phosphite, diphenyl isodecyl phosphite, diphenyldecyl phosphite, diphenyl tridecyl phosphite, among others, tris-2,4-di-tert-butylphenyl phosphite. The use of phyto is preferred.

Examples of the compound represented by the general formula (I+) include tetraphenyl dipropylene glycol diphosphite, tetralauryl bisphenol A diphosphite, tetratridecyl bisphenol A diphosphite, tetraphenyltetratridecyl pentaerythritol tetraphosphite, etc. It will be done. Among them, tetralauryl bisphenol A diphosphite is preferred.

Examples of the compound represented by the general formula (III) include diisodecyl pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, dinonylphenyl pentaerythritol diphosphite, and the like. Among them, dinonylphenylpentaerythritol diphosphite is preferred.

These phosphite compounds (C) are added in an amount of 0.05 parts by weight per 100 parts by weight of the amorphous copolyester resin (A).
It is used in a proportion of ~5 parts by weight, preferably 0.1 to 2 ffi parts. If the amount is less than 0.05 parts by weight, the adhesion retention during painting and durability when used at high temperatures will be insufficient, and if the amount is more than 5 parts by weight, the initial adhesive strength will be low.

The resin composition is further combined with the hindered phenol compound CD) represented by the formula (IV) and the phosphite compound (C) represented by the formula (I), (II) or (III). Metal laminates using resin compositions added in similar proportions also have outstanding baking properties, adhesive strength retention during painting, and durability when used at high temperatures.

- Examples of compounds represented by formula (IV) include 2゜6-
Di-tert-butyl-p-cresol, 2.5-di-tert-butyl-4-ethylphenol, 2.27-methylene-bis-4-methyl-6-tert-butylphenol, 4,4'
-methylene-bis(2,6-di-tert-butylphenol)
, 4,4-butylidene-bis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), bis(3-methyl-4-
Hydroxy-5-tert-butylbenzyl) sulfide, 4
4'-thiobis(6-tert-butyl-0-cresol)2
．． 2'-thiobis(4-methyl-6-tert-butylphenol), diethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, n-octadecyl-
3 (3',5'-di-tert-butyl-hydroxyphenyl)
Propionate, hexamethylene glycol-bis[β
-(3,5-ditert-butyl-4-hydroxyphenol)propionate], N, N'-hexamethylene-
Bis(3,5-di-tert-butyl-4-human oxyhydrocinnamic acid ado), 2,2'-thio-[diethyl-bis-3
(3,5-di-tert-butyl-4-hydroxyphenyl)propione, dioctadecyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, tetrakis[methylene-a+: 3', 5'-ditert-butyl-4'-hydroxyphenyl)propionate tocomethane, 1. 3. 3-1 Li-methyl-2
゜4.6-Tris(3',5'-di-tert-butyl-4'-
hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl-oxyethyl]isocyanurate, etc. Among these, tetrakis[methylene-3(3;5'-di-tert-butyl-4'-hydroxyphenyl)propionate comethane, 1.
3. 5-trimethyl 2, 4. 6-tris (3',
51-Ditert-butyl-4'-hydroxybenzyl)benzene is preferred.

These hindered phenol compounds (D) are used in a proportion of 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the amorphous copolyester resin (A). used. If the amount is less than 0.05 parts by weight, the adhesive strength during painting and durability when used at high temperatures will not be sufficient, and if the amount is more than 5 parts by weight, the initial adhesive strength will be low.

The resin composition used in the metal laminate of the present invention may include calcium carbonate, barium sulfate, clay, titanium oxide, silicon oxide, mica powder, fillers such as glass peas, carbon fiber, glass, etc., within a range that does not impair the original purpose. It can contain reinforcing agents such as fibers, ceramic fibers, aramid fibers, and potassium titanate fibers, various metal powders such as stainless steel powder and aluminum powder, various coupling agents, and other thermoplastic resins.

The method for producing the metal laminate of the present invention is not particularly limited, but for example, a compound (B) and a phosphite compound (C), and in some cases a hindered phenol compound, are added to an amorphous copolymerized polyester resin solution. After adding the compound (D) and mixing thoroughly, apply it to the mound layer surface of at least one, preferably both, of the metal plate, and apply at room temperature, preferably 100 to 2
After heating at a temperature of 20°C to distill off the solvent, they are bonded using a heated roll or hot press. A composition obtained by tri-blending a dark amorphous copolymerized polyester resin with a compound (B) and a phosphite compound (C) (in some cases a hindered phenol compound CD), and then heating and melt-mixing the mixture. The thickness of the resin composition layer of the present invention is 5 to 800 μm1, preferably 30 to 800 μm1.
It is 300 μm.

Further, the types of the two metal plates are not particularly limited, and may be the same or different.

Specific examples of metal plates include steel plates, aluminum plates, copper plates, etc., with steel plates being particularly preferably used.

The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

[Example] The present invention will be explained below with reference to Examples. Note that all parts in the examples are based on weight.

Furthermore, each measurement item shown in the Examples and Comparative Examples was conducted according to the following method.

-Glass transition temperature: Measured by DSC.

- Relative viscosity: 0.125 g of resin was dissolved in 25 ml of 0-chlorophenol and measured at 25°C.

・Adhesive strength: The shear strength at 6 tensions of the overlapping part of 25 m x 15 sheets was measured using a Tensilon tensile tester at a tensile speed of 20
Measured in u/sin.

・Painting resistance: Adhesive test piece heated to 220℃ or 2
The adhesive strength was measured after heat treatment for 1 hour in a hot air oven at 30°C.

- Durability: The adhesive strength was measured after heat treating the adhesive test piece in a hot air oven at 200°C for 1000 hours, 2000 hours, or 3000 hours.

The contents or chemical structures and abbreviations of the compounds used in the examples are as follows.Reference Example 404 parts of dimethyl terephthalate, 373 parts of dimethyl isophthalate, 8 parts of ethylene glycol 2G, and 300 parts of neopentyl glycol were combined with 0.34 parts of zinc acetate. Pour into a reaction vessel equipped with a stirrer and a rectification tube, and heat to 100°C.
The transesterification reaction was carried out for 3 hours from 6 to 240°C. Next, the transesterification reaction was carried out in a reaction vessel equipped with a helical ribbon stirring blade, and after adding 0.16 parts of antimony trioxide, the temperature was raised and the pressure reduced for about 1 hour according to the program. 275℃, l
The reaction conditions were brought to below uHg and kept in that state for 2 hours.
Polycondensation reaction was carried out for 0 minutes. The obtained copolymerized polyester resin (A-1) was pale yellow and transparent, and as a result of compositional analysis by NMR, the U component was terephthalic acid/isophthalic acid = 52/
48 (molar ratio), glycol component is ethylene glycol/neopentyl glycol = 55/45 (molar ratio)
As a result of thermal analysis by DSC, it was found to be an amorphous polymer with a glass transition temperature of 69° C. and a relative viscosity of 1.31.

Copolymerized polyester resins (A-2) to (A-4) whose compositions are shown in Table 1 were produced in the same manner.

(Left below) Examples 1 to 12 Copolymerized polyester resins (A-1) to (A
-4) Methyl ethyl ketone/toluene (20/80)
Each compound shown in Table 2 was added to the solution (solid content concentration 30%) in an amount shown in Table 2 based on 100 parts of the copolyester resin. This solution was applied to a chromate-treated steel plate with a thickness of 0.4 mm to a dry thickness of 25 μm, and after drying with hot air at 200°C for 2 minutes, the coated surfaces were overlapped and heated at 190°C for 2 minutes, and a 20 kg /c
After 5 days, the initial adhesion strength was measured and the anti-seizure paintability and durability tests were conducted.

The evaluation results are shown in Table 2.

Comparative Examples 1 to 12 Comparative resin compositions as shown in Table 3 were produced using the copolymerized polyester resin solutions used in the examples, and adhered in the same manner as in the examples. Initial adhesive strength was measured and anti-seizure paintability and durability were evaluated using the same method.

Table 3 also shows the results when the copolymerized polyester resin solution itself was used.

By comparing Examples and Comparative Examples, it is clear that the metal laminates of the present invention have high initial adhesion strength, and are also excellent in seizure resistance, paintability, and durability.

(The following is a blank space) [Effects of the Invention] The metal laminate of the present invention has high initial adhesive strength, excellent anti-seizing properties, excellent paintability, and durability, and can withstand use in harsh environments.

Claims (2)

[Claims] (1) A metal laminate comprising a resin layer sandwiched between two metal plates, in which the resin layer contains 100 parts by weight of an amorphous copolymerized polyester resin (A), a polyisocyanate compound, a polyepoxy compound, and an acid anhydride. 0.5 to 20 parts by weight of at least one compound (B) selected from the following, and 0.05 to 5 parts of a phosphite compound (C) represented by the following general formula (I), (II) or (III). A metal laminate comprising a resin composition obtained by mixing parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (However, R_1, R_1′, R_1″ are carbon Numbers 1-18
-COO-, -CO in the hydrocarbon group or molecular chain
Represents a hydrocarbon group having 1 to 23 carbon atoms and having an NH-bond, and may be the same or different. m is an integer from 1 to 4. ) (2) A metal laminate comprising a resin layer sandwiched between two metal plates, in which the resin layer contains 100 parts by weight of an amorphous copolymerized polyester resin (A), a polyisocyanate compound, a polyepoxy compound, and an acid anhydride. 0.5 to 20 parts by weight of at least one compound (B) selected from the following, and 0.05 to 5 parts of a phosphite compound (C) represented by the following general formula (I), (II) or (III). parts by weight and a hindered phenol compound represented by the following general formula (IV) (
D) A metal laminate comprising a resin composition obtained by mixing 0.05 to 5 parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (However, R_1, R_1', R_1" are carbon Numbers 1-18
-COO-, -CO in the hydrocarbon group or molecular chain
Represents a hydrocarbon group having 1 to 23 carbon atoms and having an NH-bond, and may be the same or different. m is an integer from 1 to 4. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (However, R_2 is an alkyl group with 1 to 18 carbon atoms,
R_2' is the same alkyl group as R_2, and may be the same as R_2. R_3 is a single bond, carbon number 1-18
-COO-, -CON in the hydrocarbon group or molecular chain of
H-, ▲ Numerical formulas, chemical formulas, tables, etc. ▼ A hydrocarbon group with 1 to 18 carbon atoms that has any of the bonds, and X is C, S
, represents a hydrocarbon group having 1 to 18 carbon atoms, or ▲a numerical formula, chemical formula, table, etc.▼. n is an integer from 1 to 4. )