JPH0156092B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an unsaturated polyester resin laminate. An object of the present invention is to provide an unsaturated polyester resin laminate having excellent heat resistance and interlayer adhesion, and excellent adhesion to metal foil used as required. Generally, unsaturated polyester resins are made of polyhydric alcohols such as ethylene glycol, diethylene glycol, and propylene glycol, maleic acid,
α, β obtained by reacting α, β ethylenically unsaturated dibasic acids such as maleic anhydride and fumaric acid with saturated dibasic acids such as phthalic anhydride and isophthalic acid.
It is obtained by dissolving and mixing an ethylenically unsaturated polyester with a polymerizable monomer having one or more polymerizable double bonds in the molecule. However, it is manufactured by impregnating a base material with the unsaturated polyester resin obtained in this way and adding additives such as peroxide and other auxiliary materials as necessary, and curing it with ultraviolet rays, radiation, heat, etc. The resulting laminates have extremely poor heat resistance, interlayer adhesion, and adhesion to metal foils used as needed, so they can hardly be put to practical use. As a result of extensive research in order to improve these drawbacks, the present invention has been developed by impregnating a base material with an unsaturated polyester resin in which all or part of the crosslinking agent is replaced with an isocyanurate derivative having an unsaturated bond in the side chain. The laminate has excellent heat resistance and interlayer adhesion,
This was developed based on the discovery that it has excellent adhesion to metal foils used as needed. The present invention comprises a α,β ethylenically unsaturated polyester, b general formula (l, m, n are integers of 1 or 2 and may be the same or different) One or more unsaturated bonds between a part or all of the hydroxyl groups of the isocyanurate and carbon-carbon An isocyanurate derivative having an unsaturated bond in the side chain obtained by carrying out an esterification reaction with an unsaturated basic acid or its lower alkyl ester, containing a crosslinking agent other than c b as necessary. The present invention relates to a method for producing an unsaturated polyester resin laminate by impregnating a base material with an unsaturated polyester resin and curing it. The α,β ethylenically unsaturated polyesters used in the present invention include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerin, trimethylolpropane, neopentyl glycol, sorbitol, polybutadiene glycol, and 1,3-butanediol. , polyhydric alcohol such as 1,6 hexanediol, α,β ethylenically unsaturated dihydrochloric acid such as maleic anhydride, maleic acid, fumaric acid, itaconic acid, and if necessary, phthalic anhydride, isophthalic acid, terephthalic acid. , glutaric acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic anhydride, 2,6 endomethylenetetrahydrophthalic anhydride, and other saturated polybasic acids by known methods known to those skilled in the art. You can use products manufactured by. The isocyanurate derivative having an unsaturated bond in the side chain used in the present invention has the general formula (l, m, n are integers of 1 or 2 and may be the same or different) One or more unsaturated bonds between a part or all of the hydroxyl groups of the isocyanurate and carbon-carbon It is obtained by carrying out an esterification reaction between an unsaturated basic acid having the following or a lower alkyl ester thereof. The esterification reaction between the above isocyanurate and the above unsaturated hydrochloric acid or the above unsaturated basic acid lower alkyl ester is known. Although the above esterification reaction can be carried out without using a solvent, it is preferable to use a solvent such as toluene or benzene. Preferably, a catalyst such as para-toluenesulfonic acid or concentrated sulfuric acid is used. The reaction temperature is preferably in the range of 60 to 130°C. The above isocyanurate derivative is an isocyanurate that undergoes an esterification reaction with the above unsaturated basic acid by changing the molar ratio of the above isocyanurate and the above unsaturated basic acid or its lower alkyl ester. The number of hydroxyl groups can be varied. For example, if 3 moles of the above unsaturated basic acid or its lower alkyl ester are reacted with 1 mole of the above isocyanurate,
All of the hydroxyl groups of the isocyanurate are esterified with the above-mentioned unsaturated-basic acids or lower alkyl esters thereof. If 1 mol of the above unsaturated basic acid or its lower alkyl ester is used per 1 mol of isocyanurate, on average, one hydroxyl group of the isocyanurate is the above unsaturated basic acid or its lower alkyl ester. An esterified product is obtained. Usually, the unsaturated basic acid or its lower alkyl ester is used in an amount of 0.5 to 5 moles per mole of the isocyanurate. Furthermore, the number of hydroxyl groups to be esterified in the isocyanurate can be changed by changing the reaction time. In the esterification reaction, it is not necessary to use only one type of the above-mentioned unsaturated basic acid or its lower alkyl ester, and two or more types of unsaturated basic acid or its lower alkyl ester may be used. Isocyanurate derivatives are usually obtained not as a single compound but as a mixture, but in the present invention they may be used in the form of a mixture. Examples of unsaturated basic acids having one or more unsaturated groups between carbon and carbon used in the present invention include acrylic acid, methacrylic acid, crotonic acid,
Isocrotonic acid, tiglic acid, angelic acid, undecylenic acid, oleic acid, linoleic acid, lyleric acid, etc. are used. As the lower alkyl of the unsaturated basic acid having one or more unsaturated bonds between carbon and carbon, the lower alkyl esters of the above-mentioned unsaturated basic acids are used, such as ethyl acrylate, butyl acrylate, Examples include methyl methacrylate and methyl oleate. An unsaturated basic acid having one or more unsaturated bonds between carbons or a lower alkyl ester thereof may be used alone or in combination of two or more. The heat resistance, interlayer adhesion, and adhesion to metal foil of the laminate obtained by changing the type of the above-mentioned unsaturated basic acid or its lower alkyl ester, the combination thereof, and the molar ratio to the above-mentioned isocyanurate. You can change your gender. In order to obtain excellent heat resistance, interlayer adhesion, and adhesion to metal foil, it is preferable to use acrylic acid or methacrylic acid as the unsaturated basic acid. Crosslinking agents other than the above isocyanurate derivatives that may be used as necessary include styrene monomer, chlorostyrene, divinylbenzene, diallyl phthalate, diallyl phthalate prepolymer, methyl methacrylate, acrylic acid, vinyl acetate monomer, acrylamide, phenylmaleimide. , maleimide, styrene bromide, tertiary butyl styrene, ethylene bromide, and alkyl acrylates of epoxy resins. A base material is impregnated with the above-mentioned unsaturated polyester, an isocyanurate derivative having an unsaturated bond in the side chain, and an unsaturated polyester resin containing other crosslinking agents as necessary to form a laminate. Organic peroxides such as benzoyl peroxide, tertiary butyl perbenzoate, di-tertiary butyl perbenzoate, dicumyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, etc. are added to the unsaturated polyester resin as a curing agent. Further, if necessary, curing accelerators such as metal naphthenates such as cobalt naphthenate and cobalt octenoate, metal salts of octenoate, amines, and sulfur compounds are added, and polymerization inhibitors such as hydroquinone, Parabenzoquinone, 2,5 diphenylparabenzoquinone, tolbenzoquinone, monotertiary butylhydroquinone, phenol resin, etc. are added and adjusted. An unsaturated polyester resin laminate can be produced by impregnating a base material and curing the laminate. Curing is carried out at normal pressure or under elevated pressure, at normal temperature, or by heating. Alternatively, after impregnating a base material with the unsaturated polyester resin, it can be cured using ultraviolet rays or radiation. Examples of photopolymerization initiators include benzoin alkyl ether (alkyl groups include methyl, ethyl, n-propyl, isobutyl, n-butyl, isopropyl, etc.), benzophenone, benzyl, Michler ketones, methyl orthobenzoyl benzoate, chloro Thioxanthone, 2,2-diethoxyacetophenone, 2-methyloxanthone, 2,2-dimethoxy-2-phenylacetophenone, 2-isopropylthioxane, etc. are used. Furthermore, the organic peroxide, curing accelerator, polymerization inhibitor, etc. described above may be added, and curing may be performed using ultraviolet rays and/or radiation in combination with thermal polymerization. Furthermore, in producing the unsaturated polyester resin laminate, inorganic fillers such as calcium carbonate, clay, hydrated alumina, antimony trioxide, borax, milled fiber, and silica sand, and chlorinated paraffin are added to the unsaturated polyester resin. , hexabromobenzene, phosphorus and other flame retardants; and organic substances such as polyethylene, polymethyl methacrylate, polystyrene, polyvinyl acetate, polyvinyl chloride, and saturated polyester. As the base material, glass fiber cloth, glass fiber mat, various synthetic fiber cloths, various synthetic fiber mats, various natural fiber cloths, various natural fiber mats, paper, decorative paper, etc. are used. The unsaturated polyester resin may be directly impregnated into the base material.
It may be dissolved in various types of cellosolves and impregnated into a base material, and then dried. In addition, after impregnating the base material with unsaturated polyester resin, alkaline earth metal
It is also possible to make a laminate by chemically thickening with isocyanates, epoxy resins, etc., or by increasing the viscosity with ultraviolet rays, electron beams, etc. and bringing it into a B-stage state. Examples of the present invention will be described. Example 1 2.1 mol of propylene glycol, 1.0 mol of maleic anhydride, and 1.0 mol of isophthalic acid were heated and reacted at 220° C. in an inert gas stream to obtain an unsaturated polyester (A) with an acid value of 30. On the other hand, 52.2 g of tris(2-hydroxyethyl) isocyanurate, 47.6 g of acrylic acid, and 0.6 g of concentrated sulfuric acid.
g, 16 mg of phenothiazine, and 120 ml of toluene were added to a three-necked flask and reacted on an oil bath at 135°C. Water produced by the reaction was flowed out of the system as an azeotropic mixture with toluene. After 4 hours, almost the theoretical amount of water flowed out and the reaction system was cooled. After washing the reaction solution with an aqueous solution containing 2% by weight of ammonia and 20% by weight of ammonium sulfate, and then with an aqueous solution containing only 20% by weight of ammonium sulfate, 25 mg of hydroquinone monomethyl ether was added to the toluene layer, and toluene was added under reduced pressure. Remove Tris (2-
67 g of acrylic ester mainly consisting of acroyloxyethyl isocyanurate was obtained. 60 parts by weight of unsaturated polyester (A) and Tris (2-
An unsaturated polyester resin (A-) was obtained by heating and dissolving 30 parts by weight of acrylic ester mainly consisting of acroyloxyethyl isocyanurate in 10 parts by weight of styrene monomer to which 0.02 parts by weight of parabenzoquinone had been added and dissolved. . 1 part by weight of dicumyl peroxide was added to 100 parts by weight of this unsaturated polyester resin (A-), heated to about 60°C, and impregnated into a glass cloth (thickness 0.18 mm, 205 g/m ² ) so that the resin content was 45. A prepreg (A-1) of % by weight was obtained. Next, the prepreg (A-1) 9
Laminated one sheet and one sheet of copper foil (thickness 35μm), heated at 180℃
A single-sided copper-clad laminate was obtained by heating and pressing under the molding conditions of 70 kg/cm ² and 60 minutes. Comparative Example 1 Unsaturated polyester resin of Example 1 (A-)
An unsaturated polyester resin (A-) was produced under the same conditions except that 30 parts by weight of the acrylic ester used in Example 1 was replaced with styrene monomer, and a prepreg (A-2) was produced under the same conditions as in Example 1. A single-sided copper-clad laminate was obtained under the same conditions as in Example 1. Table 1 shows the properties of the single-sided copper-clad laminates obtained in Example 1 and Comparative Example 1. Example 2 40 parts by weight of the acrylic ester obtained in Example 1 to 60 parts by weight of the unsaturated polyester (A) obtained in Example 1,
An unsaturated polyester resin (B) was obtained by uniformly mixing and dissolving 0.01 part by weight of parabenzoquinone at about 80°C. To 100 parts by weight of this unsaturated polyester resin (B),
0.5 parts by weight of dicumyl peroxide and 3 parts by weight of benzoin ethyl ether were added, heated to about 80°C, and 9 sheets of glass cloth (thickness 0.18 mm, 205 g/m ² ) were laminated and impregnated to obtain a resin content of 45 parts by weight. % prepreg (B-2) was obtained. Next, the prepreg (B
-2) is irradiated with ultraviolet rays for about 60 seconds using a medium-high pressure mercury lamp (2KW), and then copper foil is laminated on top of it.
A single-sided copper-clad laminate was obtained by pressure molding at 170° C., 100 Kg/cm ² , and 10 minutes. The properties of this single-sided copper-clad laminate were measured, and the results are shown in Table 1. Example 3 56.8 g of methacrylic acid instead of 47.6 g of acrylic acid
Tris(2
- 72g of methacrylic acid ester mainly consisting of (methacryloyloxyethyl) isocyanurate
I got it. A single-sided copper-clad laminate was obtained in the same manner as in Example 2, except that 40 parts by weight of this methacrylic ester was completely replaced with the acrylic ester of Example 2. The properties of this laminate were measured and the results are shown in Table 1. The measurement method for the properties other than interlayer adhesion in Table 1 is
According to JISC 6481. Interlayer adhesion was determined by visually inspecting the state of interlayer separation at the cut end during drilling and punching. ○ indicates no delamination, × indicates delamination between layers.

[Table] The unsaturated polyester resin laminate obtained by the production method of the present invention has excellent heat resistance and interlayer adhesion, and also has good peel strength.

Claims (1)

[Claims] 1 a α,β ethylenically unsaturated polyester, b general formula (l, m, n are integers of 1 or 2 and may be the same or different) One or more unsaturated bonds between a part or all of the hydroxyl groups of the isocyanurate and carbon-carbon An isocyanurate derivative having an unsaturated bond in the side chain obtained by carrying out an esterification reaction with an unsaturated basic acid or its lower alkyl ester, containing a crosslinking agent other than c b as necessary. A method for producing an unsaturated polyester resin laminate, which comprises impregnating a base material with an unsaturated polyester resin and curing it. 2. The method for producing an unsaturated polyester resin laminate according to claim 1, wherein the unsaturated monobasic acid having one or more unsaturated bonds between carbon and carbon is acrylic acid or methacrylic acid.