JPS63277264A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain a curable resin composition having excellent hydrolysis resistance, giving a molded article having extremely excellent boiling water resistance and suitable as a bathtub, etc., by compounding a specific monomer, etc., to a side chain unsaturated polymer having (meth)acryloyl group on a side chain. CONSTITUTION:The objective composition is produced by compounding (A) 100pts.wt. of a side chain unsaturated polymer having (meth)acryloyl group bonded to a side chain through a urethane bond or ester bond, a main chain composed of carbon-carbon bond and a molecular weight of >=5,000 [e.g. a polymer of formula I (R1 and R2 are H, etc.; G is diisocyanate residue; M is 50-300; n is 70-99; m is 1-30; l is 2 or 3)] with (B) 50-150pts.wt. of a monomer copolymerizable with (meth)acryloyl group (e.g. styrene), (C) 50-250pts.wt. of glassy filler and (D) 0.01-5pts.wt. of a radical-generating catalyst (e.g. benzoyl peroxide).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a curable resin composition useful for molded products such as bathtubs, washstands, and tiles that are required to have both aesthetic appearance and water resistance, especially for artificial marble. Regarding.

[Conventional technology] Taking a bathtub as an example, the conventional method was to apply a colored gel coat and then line it with polyester resin and glass fiber to produce a single, non-transparent bathtub. there were.

However, as the required appearance and performance have become more sophisticated, the manufacturing method has also changed.

For example, transparent celestial stone-like bathtubs are manufactured by applying a transparent gel coat, then lining and laminating with glass fiber and resin, and then casting with resin mixed with fillers, and this trend is increasing. can be seen.

In some cases, gel coating is followed by casting without using glass fiber, spurring product diversification.

The problem with such molded products is that the cured resin has a good color tone (filler mixture, transparency and beauty when cured, but the appearance of these products does not turn yellow in continuous boiling tests). There should be no changes such as cloudiness.

[Problems to be Solved by the Invention] Other than the above-mentioned drawbacks, the present invention is sufficiently satisfactory even in a single-sided boiling test, which is considered to be the most severe test, that is, a continuous boiling test in which only the gel coated surface is brought into contact with boiling water. The object of the present invention is to provide a curable resin composition useful for molded articles exhibiting physical properties.

[Means for Solving the Problems] That is, in order to achieve the above-mentioned object, the curable resin composition of the present invention applies gel coating to a mold, and lines the mold with a resin composition mixed with a glass filler. When molding, as a resin composition (A) a side chain unsaturated polymer having a (meth)acryloyl group in the side chain via a urethane bond or an ester bond and whose main chain is a carbon-carbon bond;
B) a monomer copolymerizable with a (meth)acryloyl group, (C) a glassy filler, and (D) a radical generating catalyst,
This made it possible to eliminate the various drawbacks mentioned above.

[Function] Side-chain unsaturated polymers with a (meth)acryloyl group in the side chain and a carbon-carbon bond in the main chain have poor hydrolysis resistance because the main chain of the constituent molecules is a carbon-carbon bond. Excellent,
For products filled with glass filler to form a cast layer and cured, if the gel coat resin layer has a certain degree of water resistance, a boiling test will show that blistering or poor appearance due to deterioration, yellowing, or It is thought that a product that is free from whitening and has excellent transparency and color tone even after the boiling test can be obtained.

The side chain unsaturated polymer used in the present invention is a curable polymer having a (meth)acryloyl group in the side chain via a urethane bond or an ester bond, and the main chain is a carbon-carbon bond. A vinyl polymer having a functional group such as a hydroxyl group, a carboxyl group, or a glycidyl group is produced, and then the functional group is reacted with a compound that shares a reactive group that performs a urethanization or esterification reaction and a (meth)acryloyl group. Manufactured by Typical manufacturing methods and specific examples include the following.

(1) Side chain unsaturated polymer having a (meth)acryloyl group in the side chain via a urethane bond 0) JP-A-59-230019, JP-A-80-384
[A] A polymer containing a hydroxyl group in the side chain, similar to that described in Publication No. 03, and C
B] An adduct of a polyvalent isocyanate and an unsaturated monoalcohol having a (meth)acryloyl group, in which an unsaturated isocyanate having a free isocyanate group is combined with the hydroxyl group of [A] in a polymerizable monomer. Examples include curable side-chain unsaturated polymers obtained by reacting CB] with isocyanate groups.

Among them, polymers represented by the following general formula [I] are preferably used in the present invention.

[However, Ri and R2 are hydrogen or a methyl group, G represents a diisocyanate residue, M is 50 to 300,
n is 70-99, m is 1-30°g, and is an integer of 2 or 3. ] Specifically, 2-hydroxylethyl (meth)acrylate or 2-hydroxylethyl (meth)acrylate is used as a polymer containing a hydroxyl group in the side chain.
- Using a copolymer of hydroxypropyl (meth)acrylate and styrene, tolylene diisocyanate and 2-hydroxyethyl (
Most suitable are those obtained by reacting 1:1 molar adducts of meth)acrylate or 2-hydroxypropyl (meth)acrylate.

(b) the polymer containing a hydroxyl group in the side chain;
Examples include curable side-chain unsaturated polymers formed by reacting (meth)acryloyloxyethyl isocyanate.

(c) A polymer containing isocyanate in the side chain obtained by copolymerizing (meth)acryloyloxyethyl isocyanate with other vinyl monomers such as styrene and methyl methacrylate, and an unsaturated alcohol having a (meth)acryloyl group. Examples include side-chain unsaturated polymers obtained by reacting.

(2) A side chain unsaturated polymer having a (meth)acryloyl group in the side chain via an ester bond; A typical example is a side chain unsaturated polymer represented by the following general formula [n].

[However, the definitions of R1, R2, M, n and m are the same as above].

Specifically, a material obtained by subjecting a copolymer of styrene and glycidyl (meth)acrylate to an esterification reaction with (meth)acrylic acid is suitable. Also, glycidyl (meth)acrylate! It is also preferable to use allyl glycidyl ether in place of a part of .

(e) The above general formula [I
Examples include polymers represented by I].

Specifically, a material obtained by reacting a copolymer of styrene and (meth)acrylic acid with glycidyl (meth)acrylate is suitable.

(~ JP-A No. 61-258817 "Curable resin and method for producing the same") [A] Obtained by reacting 1 mole of (meth)acrylic acid with 1 mole or more of epoxy resin in the molecule (meta)
By copolymerizing a component containing an unsaturated epoxy resin having an acryloyl group and an epoxy group as at least one component and a vinyl monomer using a radical polymerization catalyst, the resulting polymer contains a polymer having an epoxy group in the side chain. A reaction mixture is prepared, and then [B] substantially equimolar (meth)acrylic acid is added to the epoxy groups remaining in the reaction mixture obtained from step [A] to cause the reaction between the epoxy groups and the carboxyl groups. Examples include side-chain unsaturated polymers obtained by carrying out this process.

Among these, polymers represented by the following general formula [m] are preferred.

(Left below) Similarly, instead of the above bisphenol type epoxy resin,
Those using novolac type epoxy resin and alicyclic epoxy resin are also preferably used.

0→ The general formula [I [I
] Examples include side chain unsaturated polymers represented by the following.

The epoxy resin used is similar to 'Biped'.

(→ Examples include side chain unsaturated polymers obtained by reacting a polymer containing an acid anhydride group in the side chain with an unsaturated alcohol having a (meth)acryloyl group.

Among them, a polymer represented by the following general formula [IV] is preferably used.

(The following is a blank space) [However, R, R2, n, m and M are as described above].

Specifically, it is obtained by using a copolymer of styrene and maleic anhydride as a polymer having an acid anhydride group, and reacting it with 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate. The one that is the best.

Furthermore, polymers free of free carboxyl groups obtained by reacting the free carboxyl groups resulting from esterification with epoxy groups or monomers sharing hydroxyl groups and (meth)acryloyl groups can also be used in the present invention. It is.

The above-mentioned side chain unsaturated polymer has a molecular size of 1 m2 or more, preferably 10,000 or more and 100,000 or less.

If the molecular weight is less than 5,000, the curability and physical properties are not necessarily sufficient, and if it is more than 100,000, the viscosity becomes high and workability becomes poor.

The ratio of (meth)acryloyl groups in the side chain unsaturated polymer is desirably 1 mol% or more and 30 mol% or less.

The most suitable range is 5 mol% or more and 20 mol% or less.

As the vitreous filler used in the present invention, for example, there can be used one sold under the trade name "Frit" by Nippon Ferro-■, or one manufactured by Togei Baroty Nisha as Glass Peas. Further, it is a flat material having a size of about 50 to 400 microns and a thickness of 2 to 10 microns, and for example, glass flakes CF manufactured by Nippon Glass Fiber (■) can also be used.

There is no particular restriction on the mixing ratio of the resin (a mixture of a side chain unsaturated polymer and a copolymerizable monomer) and the glass filler, but the glass filler should be 50 parts or more and 250 parts or more per 100 parts of the resin. The following is desirable.

If it is less than 50 parts, the meaning of using filler will be diminished, and 250 parts
When the mixture is mixed, the viscosity of the mixture tends to increase, making it difficult to work with.

The particle size of the filler is 500μ or less, and currently commercially available fillers of 10g or more and 00μ or less are sufficient.

Since the side chain unsaturated polymer is usually solid itself, it is used in a form dissolved in a monomer copolymerizable with a (meth)acryloyl group. The monomers may be added at any time, but it is convenient to have them present in the reaction system before the esterification reaction to act as a reaction solvent.

As monomers that can be used for this purpose, styrene and vinyltoluene are generally used in terms of cost and curability, but divinylbenzene can also be used in combination. In addition, for example, mono- or diesters of (meth)acrylic acid, typically methyl methacrylate, may be used.Other monomers may be used in combination.

The ratio of monomer to side chain unsaturated polymer is not particularly limited and is determined mainly from the viewpoint of workability, but
Generally, it is appropriate to use 50 parts of monomer to 100 parts of side chain unsaturated polymer = 150 parts or less, and the best ratio is 100 to 120 parts.

The resin, which is a mixture of side chain unsaturated polymer and monomer, has
It is necessary to add a commonly used polymerization inhibitor.

As the radical generating catalyst used in the present invention, commercially available organic peroxides are used, such as benzoyl peroxide, di-t-butyl peroxide, 1-butyl peroxyvivalate, t-butyl peroxy, 2-ethyl hexa ester, cimilistyl peroxydicarbonate, bis(t
-butylcyclohexyl) peroxydicarbonate, and when used in combination with an accelerator, for example, a combination of peroxyketal and quaternary ammonium salt,
Examples include combinations of ketone peroxides and organic acid salts of cobalt, and combinations of hydroperoxides and copper salts or vanadium salts.

Its usage is usually 0.01 to 5 parts per 100 parts by weight of resin.
It is a heavy part.

Colorants, thermoplastic polymers, or other fillers may be added to the curable resin composition of the present invention as needed.

It goes without saying that general-purpose curable resins such as unsaturated polyester resins and vinyl ester resins can also be used in combination without changing the physical properties.

The curable resin composition of the present invention can be manufactured into various molded products by mixing, molding, and curing the curable polymer, copolymerizable monomer, glassy filler, and radical generating catalyst using a conventional method. be done.

[Example] Next, in order to help the understanding of the present invention, examples are shown below.

Example 1 Synthesis of side chain unsaturated polymer [A] having a methacryloyl group in the side chain via a urethane bond.

In a 1 g separable flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, 312 g of styrene was added.
2-Hydroxypropyl methacrylate.

t-43g5 t-butyldodecylmercaptan 3.5g
was charged and polymerized by heating at 120 to 125° C. in a nitrogen gas stream, and the polymerization rate reached 62% in 5 hours. GPC14
According to the 11th constant, it was a polymer with a peak at a molecular weight of 27,000. After adding 0.2 g of hydroquinone, 155 g of styrene was added, the temperature was lowered to 60°C, and 40 g of isocyanate ethyl methacrylate (formula below) manufactured by Dow Chemical Company as an unsaturated isocyanate and 0.2 g of dibutyltin dilaure L were added. Add 5g, 6
After reacting at 0°C for 5 hours in a dry air stream, infrared analysis showed that the free isocyanate-1 groups had completely disappeared.

A side chain unsaturated polymer [A] which was almost colorless and had a viscosity of 6.7 poise was obtained.

Molding and boiling test of cast products.

After applying a mold release agent on a glass plate of 380 m/m x 360 m/m, 100 parts of "G-400" (containing 4% Erosil), a polyester resin manufactured by Showa Kobunshi Co., Ltd., was added as a gel coat, and Kayaku Nouri was applied as a gel coat. Add 1.5 parts of "Parriki Dox #16" [bis(4-t-butylcyclohexyl) peroxydicarbonate] manufactured by Co., Ltd., and add 0.5 to 0.
[After spraying to a thickness of 3m/m, 60°
It was gelled by heating for C1 hour.

This is used as one side, and the other side is a glass mat with a thickness of 1.2 m/m and an FRP plate using polyester resin, and fixed with a spacer of 10m/+n in thickness, and this gel coat molded glass plate and Between the FRP board and the resin for casting, 100 parts of polymer [A], 200 parts of frit M-10-8 manufactured by Nippon Ferro Co., Ltd., and Bariki Dox #1 were added.
6 was added, and the mixed resin was uniformly kneaded and defoamed, and cast.

After casting, it was cured by heating at 60°C for 1 hour and then at 70°C for 4 hours.

After curing, it was cut to 150m/m x 150rfi/m, and the surface coated with Kelcoat was brought into close contact with a boiling resistance test container with a circular hole of 12On+/m in diameter via a silicone rubber backing, and a continuous boiling test was performed. Ta.

For comparison, polyester resin [:B] (neopentyl glycol 1
0,7 mol - 4 mol of isophthalic acid to 6 mol of fumaric acid, 2
A cast plate was prepared using the step method, final acid value 34.4, styrene 45%), with all other conditions being the same.

As shown in Table 1, the results of the continuous boiling test clearly showed that the casting plate using the side chain unsaturated polymer [A] was superior.

(Left below) Table 1 Example 2 Synthesis of side chain unsaturated polymer [C] having an acryloyl group in the side chain via an ester bond.

A 2g separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a gas inlet tube was charged with 936g of styrene, 140g of glycidel methacrylate, and 10g of t-butyldodecylmercaptan, and heated to 120-125°C.
When stirred in a nitrogen stream for 6 hours, GPC measurement showed a peak for all 36,000 molecules and the reaction rate was 46%, so 0.3 g of hydroquinone was added, the temperature was lowered to 110°C, and the air system was stirred. 87 g of acrylic acid and 2 g of trimethylbenzylammonium chloride were added in a flowing stream and reacted for 3 hours. It was confirmed that the acid value was 13.4 and that the absorption of epoxy groups had completely disappeared from the infrared absorption spectrum.

A side chain unsaturated polymer [C] having a Hazen color number of 75 and a viscosity of 5.9 poise was obtained.

Production of cast products A side chain unsaturated bond type polymer [[
Uniformly mix 100 parts of C, 4 parts of Aerosil #200, and 2 parts of t-butyl peroxyvivalate,
It was coated with a bar coater to a thickness of 0.6+a/m.

Leave it at 70°C for 30 minutes and when the surface becomes non-adhesive,
As in Example 1, a glass plate coated with FRP on one side and gel coated on the other side was used as a casting mold with a spacer of thickness 10+11/II+, and the inside was filled with unsaturated polymer [C3100 parts manufactured by Togei Barotii Co., Ltd. with average particle size] 150 parts of approximately 30μ glass bulbs (trade name: EGB 31), 1 part of A-174 manufactured by Unisan Carbide as a silane coupling agent, and 1.5 parts of t-butyl peroxybiparate were added and injected. Thereafter, the film was heated at 60° C. for 1 hour and at 70° C. for 3 hours to complete curing.

A casting plate with a sense of transparency was obtained. This was subjected to a single-sided boiling test in the same manner as in Example 1.

The results were good, as seen in Table 2.

Table 2 Example 3 Synthesis of side chain unsaturated polymer [D] having a methacryloyl group via an ester bond in the side chain, 2 g equipped with a stirrer, reflux condenser, gas inlet tube with thermometer, and dropping funnel
A separable flask was charged with 728 g of styrene and log of t-butyldodecyl mercaptan, and a mixture of 200 g of methyl methacrylate and 98 g of maleic anhydride was added dropwise at a temperature of 100° C. in a nitrogen stream.

After the dropwise addition was started, the temperature was raised to 120°C, and the dropwise addition was completed at the same temperature for 5 hours.

After the dropwise addition was completed, heating was continued at the same temperature for an additional hour, and the solid content became 45 (%). In molecular weight measurement by GPC, 2
The peak was at 8,000. Lower the temperature to 100℃,
After adding 0.2 g of hydroquinone, 130 g of 2-hydroxyethyl methacrylate, and 2 g of para-toluenesulfonic acid and reacting at the same temperature for 6 hours, infrared analysis showed that approximately 70 (%) of the acid anhydride absorption in the polymer disappeared. It was determined that

Side chain unsaturated polymer with methacryloyl group in the side chain [
D] was obtained with a viscosity of 9.4 voids and a Hazen color number of 200.

Production and testing of casting plates.

A glass plate coated with gel coat as in Example 1 and FR
Between the P plates, 1100 parts of side chain unsaturated polymer CD, 8200 parts of frit S-10-8, 1.5 parts of t-butyl peroxybiparate, and 1741 parts of silane coupling agent A- were placed so that the thickness was Low/m. The mixed resin was defoamed and cast.

It was cured by heating at 60° C. for 1 hour and at 70° C. for 3 hours, so a cutting and boiling test was conducted to the same dimensions as in Example 1.

As a result of a 300-hour continuous boiling test on one side, no blisters were observed.

Example '4 Synthesis of side chain unsaturated polymer [E] having a (meth)acryloyl group via an ester bond in the side chain. As an epoxy resin, ebokite value 18
1125g of diglycidyl ether type epoxy resin No.7
, 86 g of methacrylic acid, 3 g of trimethylbenzylammonium chloride, and 0.3 g of hydroquinone were charged.
When heated and stirred at 130-135°C in an air stream, about 1.
After 5 hours, the acid value became practically zero, so styrene 29
0 g was added to obtain unsaturated epoxy resin [I].

In a similar device prepared separately, unsaturated epoxy resin [I]
300g of methacrylic acid, 1000g of styrene were heated at 120°C for 6 hours in a nitrogen gas stream to make the solids approximately 46%, and then 88g of methacrylic acid, 2.7g of trimethylbenzylammonium chloride, and 0.5g of hydroquinone were added.
, and reacted for 3 hours at 110 to 115°C in an air stream, the acid value was 11.4, so 114 g of styrene was added, and the side chain unsaturated polymer [E] was converted to Hazen color number. 250 with a viscosity of 3.7 poise.

To 100 parts of side chain unsaturated polymer [E], 1.5 parts of Perryoku Dox #16 (trade name, manufactured by Kayaku Nouri Co., Ltd.) was added, and glass flakes such as CF-150 (Nippon Glass Fibers) were added.
After adding 70 parts of Silane Coupling Agent A-1742 parts and defoaming under reduced pressure, the same gel coat as prepared in Example 1 was injected between FRP plates and cured at 60°C for 1 hour, then at 70°C for 4 hours. It was made into a casting board.

In continuous boiling on one side, no blistering or cracking was observed even after 1000 hours, and no whitening of the cast layer was observed.

Example 5 Production of side chain unsaturated polymer [F] having (meth)acryloyl group in side chain via urethane bond 3! Predetermined amounts of styrene, hydroxyethyl methacrylate, t-dodecyl mercaptan, and n-dodecyl mercaptan were charged into a :1 autoclave, and copolymerization was carried out at a predetermined temperature. Samples were taken periodically and the molecular weight was determined.

When a predetermined molecular weight was reached, a predetermined amount of a diluent consisting of styrene as a diluent monomer, hydroquinone as a polymerization inhibitor, and dibutyltin dilaurate as a catalyst was poured into an autoclave, and the mixture was stirred for 0.5 hours while maintaining the temperature at 60°C. Ta.

Next, 130 parts of tolylene diisocyanate and 150 parts of 2-hydroxypropyl methacrylate were reacted, and an equivalent amount of an unsaturated isocyanate sharing a methacryloyl group and an isocyanate group was added to the molecule obtained by reacting 130 parts of tolylene diisocyanate with 150 parts of 2-hydroxypropyl methacrylate.
The notanization was carried out at °C until the isocyanate groups disappeared. The reaction time was approximately 6 hours.

A peroxide catalyst (manufactured by NOF HOME CO., LTD., VIRGURE 5A) was added to the ioo portion of the obtained side chain unsaturated polymer [F]. 5 parts and 0.5 parts of cobalt naphthenate (containing 6% cobalt) were blended and cured at room temperature, and the physical properties were measured.

(Margins below) Table 3 Production of gel coat 100 parts of side chain unsaturated polymer [P], Erosil Rx
4 parts of -200 and 0.02 part of phthalocyanine blue were roll-kneaded and gel coated.

Preparation of test piece On a glass plate treated with a mold release agent, add 1.5 parts of Parriki Dox +16 to 100 parts of gel coat at 0.6 m/m.
After coating with a bar coater so that
Glass Surface Mat 30p was impregnated with a resin solution prepared by adding 5 parts of Erosil Rx-2001 and 161 parts of Verkadox #1, and applied next to the gel coat layer, and heated at 60°C for 30 minutes to gel. I let it happen. The thickness of the intermediate layer was approximately 0.8 mm.

This was used as one side, and the other side was an FRP plate using glass mat with a thickness of 1 to 1.5 m/a+, and 100 parts of side chain unsaturated polymer [F] was added to the plate so that the thickness was about 8 m/rn. A casting composition containing 200 parts of Frit MIO-8 and 1 part of Parkadox #16 was cast, initially at 60°C for 1 hour.
It was cured by heating at 70°C for 4 hours.

When one-sided boiling was carried out in the same manner as in Example 1, no blistering or whitening was observed even after 500 hours.

[Effects of the Invention] The curable resin composition of the present invention can be used to produce various molded products with extremely excellent boiling resistance at low cost, and can be used to improve the water resistance of bathtubs, bathroom vanities, tiles, etc. Very useful for applications that require aesthetic appearance.

Claims (1)

[Claims] (A) Through a urethane bond or an ester bond in the side chain (
(meth) A side chain unsaturated polymer having an acryloyl group and whose main chain is a carbon-carbon bond, (B) A monomer copolymerizable with the (meth)acryloyl group, (C) A glassy filler, and (D) A radical generating catalyst. A curable resin composition consisting of: