JPS6048346A - Manufacture of resin composite body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a resin composite comprising a styrenic thermoplastic resin, an unsaturated polyester resin and/or a vinyl ester resin.

Styrenic thermoplastic resins such as polystyrene resins, acrylonitrile-styrene resins, ABS resins, etc. are excellent in cost and performance and are used in various fields. However, since it is thermoplastic, it may deform due to heat.
It is easy to cause creep failure, and foamed molded products have problems with strength, surface hardness, etc., and their uses are limited.

Conventionally, various attempts have been made to overcome the above-mentioned drawbacks, but the current situation is that nothing satisfactory has been achieved. For example, unsaturated polyester 4HllFr
The surface of a styrene-based thermoplastic resin molded product is coated with Yabinyl-S resin to improve its solvent resistance and thermal properties, and even a fibrous reinforcing material is used in conjunction with the coating to improve so-called F)1. One example is an attempt to improve mechanical properties by adding P. However, when using this method, if an attempt is made to cure an unsaturated polyester resin or vinyl ester resin in contact with a styrene photothermal 0Tf11 resin, the surface of the thermoplastic resin or the entire molded article will be significantly eroded before it is cured. is extremely difficult to achieve.

Therefore, the present inventor took into account the shortcomings of the conventional method, and developed a method using a styrenic thermoplastic resin and an unsaturated polyester resin.
Or fX for resin combination with vinyl ester resin: As a result of intensive research to make it possible, the present invention was completed.

That is, the present invention provides a styrenic thermoplastic resin molded product (1
) After applying and curing the primer (■) shown below on the surface of the unsaturated polyester resin (
Ill-1) and/or vinyl ester resin (Ill-1)
2) is applied or laminated together with a filler or a fibrous reinforcing material if necessary, and cured.

A primer (1'l) comprising a compound (A) represented by the general formula (a), an unsaturated polyester (B), and optionally a polymerizable monomer <C> other than the compound (A).

General formula (a) O 1 It is related to.

In this specification, (meth)acrylate means acrylate and/or methacrylate, and (meth)acrylic acid means acrylic acid and/or methacrylic acid.

The styrenic thermoplastic resin molded article (1) refers to a molded article of styrene polymer or styrene copolymer. For example, polystyrene resin, acrylonitrile-butadiene-styrene resin (ABS411 resin), acrylonitrile-styrene resin (A8 resin 11W), acrylonitrile-acrylate styrene resin (AAS resin), methyl methacrylate-butadiene-styrene resin (MH8 resin)
Can you name some molded products? There are no particular restrictions on the shape of the molded product, such as flat plate, sheet, Glock, etc.
There are molded products with specific shapes, foam molded products, etc. Among these styrene-based thermoplastic resin molded products, the effects of the present invention are greater and more preferable when polystyrene resins and ABS resins are used. This is preferable because the effects of the present invention are most effectively exhibited.

As described above, the primer (n) is composed of the compound (A), the unsaturated polyester (I3), and the optional polymerizable monomer (C).

Compound (A) is a polyfunctional (meth) compound represented by the general formula (a) and having two or more acryloyloxy groups in the molecule.
As such a compound (A) which is an acrylate,
Diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetraglobile/glycol di(meth)acrylate Acrylate, glycerin (
meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane di(meth)acrylate, trimethylolethane tri(meth)acrylate, pe/ Examples include taerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc.
One or more of these may be used.

Among these (meth)acrylates, those that are liquid at room temperature are preferred.

The unsaturated polyester (13) contains α,β-unsaturated carboxylic acid ester and has a molecular weight of about 3oO to 5000
Polyester. The content h1 of the α,β-unsulfated carboxylic acid ester group is so vague as to be at least 3 moles, preferably 7 moles or more, based on the total ester groups in the unsaturated polyester (13). Such unsaturated polyester (13) can be easily produced according to conventionally known methods. For example, α,β-unsaturated dicarboxylic acid and/or its anhydride are essential as the acid component, saturated dicarboxylic acid and/or its anhydride are used as necessary, and glycol and/or as the alcohol component.
Or produced using alkylene oxide, which is a glycol precursor, as the main component in the presence or absence of a catalyst in an inert gas atmosphere at a temperature range of 100 to 250°C.
A method in which a part of the acid component in the above method is replaced with a monocarbo/acid or a trifunctional or more functional polycarbo/acid as a functional agent; A method of reacting with an epoxy compound containing an α,β-unsaturated 40 carboxylic acid ester group represented by methacrylate; as an acid component, a saturated dicarboxylic acid and anhydride of bamboo shoots and, if necessary, a monocarboxylic acid, etc. This method involves reacting a terminal carboxylic acid type saturated polynisder obtained using a modifier with an epoxy compound having an α,β-unsaturated norboxylic acid ester group represented by glycidyl methacrylate.

The filtrate components used when producing unsaturated polynisder (B) include α, β-, β-dicarboxylic acids such as maleic anhydride, fumaric acid, and itaconic acid; phthalic anhydride, terephthalic acid, inphthalic acid, and succinic acid. acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-
Examples include saturated dicarboxylic acids such as nindomethylene/tetrahydrophthalic anhydride, 3,6-nindomethylene/hexachlorophthalic anhydride, and adipic acid. Alcohol components include alkylene/glycol angles such as ethylene glycol, propylene glycol, neopentyl glycol, and 1,6-hexanediol; polyalkylenes such as diethylene glycol, triethylene glycol, diethylene glycol, triprobe/glycol, polyethylene glycol, and polypropylene/glycol. Glycols: Alkylene oxides such as ethylene oxide, propylene oxide, epichlorohydrin, allylglycidyl ether: Addition reaction products of polyphenols such as bisphenol A and alkylene oxides, trimethylolethane monoallyl ether, be/taerythritol diallyl ether , glycerin monoallyl tetyl, trimethylolethane monoallyl ether, and other allyl ether group-containing glycols.

Modifiers include hexyl alcohol, tetrahydrofurfuryl alcohol, 8(9)-hydroxy-tricyclo[5,2,1,02)6]deca-3-yne, trimethylolpropane diallyl needle, glycerin diallyl ether. , allyl cellosolve, addition reaction products of allyl alcohol and alkylene oxide; monohydric alcohols such as glycerin, trimethylolpropane, pentaerythritol monoallyl ether, pe/taerythritol, tris(2-hydroxyethyl) cyanurate, etc. Examples include polyhydric alcohols with higher valences.

Among the unsaturated polyesters (B) thus obtained, at least 10 moles of the acid component, preferably 20
tetrahydrophthalic acid, methyltetrahydrophthalic acid, 3°6-nindomethylenetetrahydrophthalic acid or their anhydrides in mole proportions, and at least 20 moles, preferably 30 moles of alcohol component.
Polyalkylene/glycol at a ratio of more than molti? f
unsaturated polyester (B-1) derived using il, and low allyl ether group content (both 0.1/
1000. allyl ether group-containing glycols in a proportion such that the total amount is preferably 71,000 g,
Allyl glycidyl ether, trimethylolpropane diallyl ether, glycerin diallyl ether, allyl selon, addition reaction product of allyl alcohol and alkylene oxide, pentaerythritol monoallyl ether, etc. (B-2)
) is preferable because it quickly develops adhesive strength with the styrene thermoplastic resin molded product (+). Furthermore, among them,
Polyalkylene/glycol such as diethylene glycol, triethylene glycol, polyethylene glycol, etc.
represents an integer. The unsaturated polyester (B-1) derived from a glycol represented by the general formula (B-1) is particularly preferable, and among these, glycidyl methacrylate is used as a part of the glycol component and/or as a terminal modifier.
The one derived from the above is more preferable.

Polymerizable monomers (C) other than compound (A) that may be used as necessary include methyl/, chlorostyrene, vinyltoluene, methyl (meth)acrylate, and ethyl (meth)acrylate.
Acrylate, phytyl(meth)acrylate, octyl(meth)acrylate, ethylene glycol di(meth)acrylate, propylene/glycol di(meth)acrylate, hexyl/glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc. Is or 2i4 or more of these compounds can be appropriately selected and used.

Primer (II) is composed of the above-mentioned compound (A), unsaturated polyester (B) and, if necessary, a polymerizable monomer (C).
The weight ratio of compound (A) and unsaturated polyester (B) is 9
/1 to 1/9, and the polymerizable monomer (C
) is used when the total weight of compound (A) and unsaturated polyester (H) is 40 inches or less. If the ratio of compound (A) and unsaturated polyester (13) is outside the above range, the curing speed at room temperature may be slow or the primer (11) may
This is not preferable because the viscosity IW increases too much.

The proportion of the polymerizable monomer (C) used is as described above.

However, for example, styrene compound (A)
When the total weight of unsaturated polynisdel (B) is 30, polystyrene foam molded product and primer (II) Y
It is undesirable because it corrodes the surface of the polystyrene foam molded product in a short period of time when it comes into contact with it. That is, polymerizable monomer (
Types of C) and styrene thermoplastic resin molded products (1)
An appropriate range for use is determined within the above range depending on the type and shape of the material.

In preparing the primer (11), various additives known in the unsaturated polyester resin industry are used, such as gelling modifiers, storage stabilizers, curing accelerators, antifoaming agents, leveling agents, surface driers, Ultraviolet absorbers, chicken-like agents, etc. can be effectively used.

The primer (II) thus obtained can be cured using a polymerization initiator commonly used in the art.

As a polymerization initiator, t-butyl hydroperoxide, cumene hydroperoxide, hendiyl peroxide, 2,4-
Examples include peroxides such as dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, t-butyl perve/shade, and methyl inbutyl ketone peroxide, and if necessary, a curing accelerator may be used in combination with the polymerization initiator. can. Organic amines such as aliphatic amines and aromatic amines as curing accelerators: cobalt naphthenate, cobalt octenoate, vanadium acetonate,
Examples include organic metal salts and chelates such as cobalt acetonate.

Furthermore, it can be cured by using a photosensitizer and ultraviolet rays, or by irradiation with electron beams or the like.

One method of using the primer (n) is to coat the surface of the styrene thermoplastic resin molded product (1) with a brush roll coater.
, flow coater, sougere, chipping and other known methods to achieve a thickness of at least 0.01, preferably 0.
．． There is a method of coating and curing in order of 04 or higher. At this time, if necessary, fillers, colorants, reinforcing materials, patterned materials such as printed paper, etc., known in the art may also be used.

Primer (II) applied to the surface of the styrenic thermoplastic resin molded article (1) in this manner. The molded article (1) is cured at room temperature or under mild heating to the extent that the molded article (1) does not deform.

The degree of curing at this time does not necessarily mean that the primer (11) is completely cured (in addition, the surface of the primer (11) is coated with unsaturated polyester resin (III-1) or vinyl ester resin (11)).
-2) When applying and curing V, before these resins are cured, the main reactive monomers in them, such as styrene and aromatic vinyl compounds such as vinyltoluene, are molded from styrene thermoplastic resins. It is sufficient that the hardening is sufficient to prevent the product (1) from being eroded. For example, the degree of curing of primer (n) may be relatively low if the primer (It) is applied in a small amount or if the subsequent resin cures quickly; conversely, if the amount of primer (11) applied is small or If the curing of the subsequent resin is slow, the degree of curing of the primer (n) must be higher. Therefore, the minimum required degree of curing of the primer (II) varies depending on each case, but it is can be easily determined by carrying out simple experiments in each case, and the present invention is not affected by this difference in degree of curing.

As the unsaturated polyester resin (III-1) and/or the vinyl ester resin (1-2), conventionally known ones can be freely used, but among them, styrene and When using a resin containing an aromatic vinyl compound such as vinyltoluene, the effects of the present invention are most effectively exhibited.

Examples of unsaturated polyester resins ([-1) are listed in the section on the chemistry of 2° unsaturated polyester resins, "Polyester Resins" by Eiichi Takiyama (February 28, 1970, published by Nikkan Kogyo Shimbun). I can list things that have been done. Examples of vinyl ester resins (III-2) include "Reaction of epoxy resin and polymerizable monomer carboxylic acid," which is described in detail as "epoxy ester resin" in Patent Publication No. 7791 of 1979. The product or the reaction product of the epoxy resin and carboxylic acids and/-! or carboxylic acid anhydrides containing polymerizable unsaturated carboxylic acid as a main component is dissolved in a polymerizable unsaturated monomer. Thermosetting resins” can be mentioned.

When using unsaturated polyester resin (Ill-1) and vinyl ester resin (ll1-2), it is possible to effectively utilize commercially available products or according to methods conventionally known in the unsaturated polyester resin industry. .

For example, a filler, a coloring agent, a reinforcing material, a patterned material such as a printed paper, etc. can be used, and a hardening agent can be applied or laminated using a hardening agent, if necessary, along with a hardening accelerator, and then hardened.

The resin composite obtained according to the method of the present invention has a styrenic thermoplastic resin layer and an unsaturated polyester resin and/or vinyl ester resin layer with primer (II) Y
The thermal, mechanical, and chemical properties of the styrenic thermoplastic resin molded product (1) have been greatly improved, and the application fields of the molded product (1) have been greatly improved. It can be expanded in width.

Hereinafter, the present invention will be explained in more detail with reference to examples.

It should be noted that the term "part" in the description refers to the single-layered heel 1.

Example 1 Maleic anhydride, cono-phosphoric acid, diethylene glycol and propylene glycol were reacted in a molar ratio of 0.6:0.4:0.6:0.6, respectively, according to a conventional method to give an acid value of 27. unsaturated polyester/l/
(fIi Riester (1)) 'a? Obtained. Next, 1,160 parts of polyester, 40 parts of trimethylolgulonosine triacrylate, 70.02 parts of hydroquino, 0.05 part of paraffin, and 10 parts of styrene were uniformly dissolved to obtain a primer (II-1).

100 parts of primer (II-1), 1.0 part of cobalt octenoate (containing metal, the same applies hereinafter) and methyl ethyl ketone peroxide (155
Apply a resin liquid containing 1.5 parts of NS (the same applies hereafter) to the north face of a 30x expanded polyester/foam plate to a thickness of approximately 5.
After coating to give a coating thickness of 0()μ, it was left to stand at room temperature. Primer (11-1) gelled 30 minutes after blending with methyl ethyl ketone peroxide, and after 5 hours of gelation, the interior of primer (It-1) was hardened although the surface was somewhat sticky.

Next, unsaturated polyester resin (Japan Square Width Theta Cutting Chemical) Nigyo (stock system, Ebola Nku G-753P TM
) 100 parts of resin solution containing 1.0 parts of methyl ethyl ketone peroxide and glass fiber (Nittobo (Membrane MC-1)
450A)'r, the resin liquid and glass fiber are
FRP so that the Fic ratio is about 70:30 and the thickness is 3 questions.
was laminated and molded. After 5 hours, the resin composite was substantially completely cured to 91F Ph and was firmly integrated with the polystyrene foam. Later, when this resin composite was cut and inspected, it was found that the entire styrene foam layer (1) was not eroded.

Example 2 Maleic anhydride, tetrahydrophthalic anhydride and diethylene glycol were prepared in a molar ratio of 0 according to a conventional method.
．． An unsaturated polyester (2) with an acid value of 23 was obtained at a ratio of 7:03:1.2.Next, polyester (2160 parts, 40 parts of methylolpropane triacrylate) was obtained. ,) Amateur Kino 70.02
1 part and 5 parts of styrene were uniformly dissolved to prepare primer (I).
I-2)'r obtained.

100 parts of primer (It-2), 1 part of octene, 1.0 part of cobalt, and 1 part of methyl ethyl ketone oxide
．． A resin solution containing 5 parts of the resin solution was applied to the north face of a 30 times expanded 1-sheet styrene foam plate to a thickness of about 200 μm per plate, and then allowed to stand at room temperature. Approximately 42 minutes after mixing methyl ethyl ketone oxide, primer (II
-2) gelatinized, and after 4 hours of gelation, it was uniformly hardened to the surface.

Next, FI (P) was laminated and molded on the top surface in the same manner as in Example 1 to obtain a resin composite. When this resin composite was tested in the same manner as in Example 1, it was found that the entire polystyrene foam layer was (It was not eroded.

Example 3 608 parts of tetrahydrophthalic anhydride and 318 parts of diethylene glycol were esterified according to a conventional method,
When the acid value reached 126, it was 5 series y! l-110℃
190 parts of styrene, 3 parts of triethylamine, 5 parts of [1-hydroquinone] and 280 parts of glycidyl methacrylate were added and reacted at 110°C until the acid value was 1.
6, 770 parts of triethylene glycol dimethacrylate was added to obtain primer (II-3).

Primer (n-3) cobal octenoate in the loop part) 2
．． 0 parts and 1.0 parts of methyl ethyl ketone (-oxide)
A polystyrene foam with a thickness of 20 mm and a thickness of 60 times was applied to the resin liquid to a coating thickness of about 60 μm, and then cured at room temperature for 3 hours. Next, FRPy was laminated to a thickness of about 3 mm on the surface in the same manner as in Example 1 to obtain a resin composite having a core of expanded polystyrene and a surface of FILP.

Example 4 392 parts of maleic anhydride and 2 parts of Zorobire/Glycol
After esterifying 28 parts in a conventional manner and raising the reaction temperature to 130°C when the acid value reached 191, 228 parts of allyl glycidyl ether, 3.7 parts of hydroquinone and 1.5 parts of triethylamine were added. The reaction was carried out at 130°C, and when the acid value reached 21, 185 parts of tetraethylene glycol cyacrylate and 100 parts of styrene were added to obtain a primer (It-4).

100 parts of primer (II-4) and cobalt octoate
, og and 1.0 part of methyl ethyl ketone peroxide was expanded 60 times to 600 x 300 x 40.
The coating thickness is approximately 100μ on the entire surface of the polystyrene foam.
It was applied and cured at room temperature for 5 hours. Next, apply vinyl ester resin (manufactured by Nippon Kaihoku Kagaku Kogyo ■) to the surface.
100 parts of Eporac RF-1001) and 0.0 parts of paraffin.
1 part, 0.1 part of octe/cobalt acid, 0.1 part of dimethylaniline and 1 part of methyl ethyl ketone peroxide,
5 parts of resin liquid and glass fiber (MC- manufactured by Nittobo)
45OA) in the same manner as in Example 1, FRP was laminated and molded to obtain a resin composite.

Actual Example 5 In Actual Example 3, tetrahydrophthalic anhydride 608
A primer (1-5) having an acid value of 12 was obtained in the same manner as in Example 3, except that 304 parts of tetrahydrophthalic anhydride and 196 parts of maleic anhydride were used instead of f@S.

2.0 parts of cobalt octenoate and 1.0 parts of methyl ethyl ketone peroxide to 100 parts of primer (I+-5)
A resin solution containing 30% of the foam was applied to both sides of a 30x foamed polystyrene foam plate to a coating thickness of about 60μ, and after curing at room temperature for 4 hours, the same procedure as in Example 1 was carried out. Then, FRP was laminated and molded on both sides to obtain a resin composite having a Zandwich structure, in which both sides were F'RP and the core was polystyrene foam.

Example 6 A composition prepared by blending 1.00 parts of the primer (1-5) obtained in Example 5 with 100 parts of calcium carbonate powder, 20 parts of cobalt octenoate, and 10 parts of methyl ethyl keto/peroxide was foamed to a thickness of 30 times after 100 times foaming. The coating of Example 1 was applied to both sides of Dragon's polystyrene foam plate to a coating thickness of about 500 μm, and after curing at room temperature for 90 minutes, Example 1 was applied to both sides of the plate.
In the same manner as in the above case, a resin composite having a glass/deutsch structure was obtained by laminating FRPY to a thickness of about 2.0 mm and having FR and P on both sides and a polystyrene foam core.

Example 7 Double-sided fabrication was carried out in the same manner as in Example 5, except that instead of the polystyrene foam flat plate, a 2 mm thick ABS resin flat plate (ABS molded product) was used. was Fl(, P) and a resin core with a Su/Deutsch structure in which the core was made of ABS resin was obtained.

Claims (1)

[Claims] 1. After applying and curing the primer (II)' shown below on the surface of the styrene thermoplastic resin molded product (1), unsaturated polyester resin (IN-1
) and/or vinyl ester resin (ffl-2) is coated or laminated together with a filler or fibrous reinforcing material if necessary, and cured.
Method. A primer (n) comprising a compound (A) represented by the general formula (a), an unsaturated polyester (B) and, if necessary, a polymerizable monomer (C) other than the metal compound (A). General formula (a) 0 1