JPH05301934A - Resin composition and laminate product and composite product using the same - Google Patents

Abstract

PURPOSE:To provide the heat-resistant resin composition comprising a novolak epoxy (meth)acrylate resin, a polyfunctional (meth)acrylate ester and a copolymerizable monomer, giving cured products excellent in the organic solvent resistance and hot water resistance, and useful for fiber-reinforced resin laminate products, etc. CONSTITUTION:The objective resin composition giving cured products having a thermal deformation temperature of approximately 200 deg.C, excellent in the organic solvent resistance and hot water resistance and useful for fiber- reinforced resin laminate products, composite products, etc., comprises (A) 100 pts.wt. of a novolak epoxy (meth)acrylate resin, (B) 20-80 pts.wt. of a multifunctional (meth)acrylate ester (e.g. ethylene glycol dimethacrylate) of the formula (R<1> is H, methyl; R<2> is 2-20C di- to hexa-valent polyhydric alcohol residue; (m) is an integer of 4-0 l+m=2-6), and (C) 10-70 pts.wt. of a monomer (e.g. styrene) having one or more of copolymerizable double bonds in the molecule or its mixture (excluding monomers belonging to the component B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novolac epoxy (meth) acrylate resin having improved heat resistance and corrosion resistance, and a fiber-reinforced resin laminate and composite using the same.

[0002]

2. Description of the Related Art Conventional vinyl ester resins have excellent mechanical properties, electrical properties, heat resistance, high adhesiveness and good molding processability, and further have excellent chemical resistance, especially oxidation resistance. It is widely used as a matrix (base material) of equipment materials, especially glass fiber and other fiber reinforced corrosion resistant fiber reinforced plastic (FRP). For example, chemical solution storage tanks, tanks, pollution control equipment or piping in chemical plants. It is widely used for materials such as. However, due to the expanded use of FRP, a resin having higher heat resistance and corrosion resistance and room temperature workability has been required.

In order to achieve the above-mentioned object, the present applicant previously prepared a resin composition in which a relatively large amount of a polyfunctional (meth) acrylic acid ester was blended with a novolac type epoxy (meth) acrylate resin as a fibrous reinforcing material. It has been proposed about a laminate which is impregnated and cured (JP-A-3-134028). However, although the resin composition described here is excellent in heat resistance and organic solvent resistance, it has been found that there is a problem in hot water resistance.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition having heat resistance as well as organic solvent resistance and hot water resistance without deteriorating the excellent properties of vinyl ester resin, particularly the workability at low temperature. The present invention also provides a composite obtained by laminating and curing the impregnated body on a fibrous reinforcing material and a fluororesin sheet impregnated with the resin composition.

[0005]

Means for Solving the Problems As a result of various investigations on the resin described in JP-A-3-134028, the present inventors have found that one of the components, a polyfunctional (meth) acrylic acid ester, The present invention has been completed by finding that the above object can be achieved by reducing the compounding ratio with respect to a novolac type epoxy (meth) acrylate resin.

The present invention comprises: a) 100 parts by weight of a novolac type epoxy (meth) acrylate resin b) 20 to 80 parts by weight of a polyfunctional (meth) acrylic acid ester represented by the general formula (I) or a mixture thereof.

[0007]

[Chemical 2]

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a polyhydric alcohol residue having 2 to 20 carbon atoms and 2 to 6 valences, and m represents an integer of 2 to 6, l is 4
Represents an integer of 0, and 1 + m = 2-6. C) Monomers having one or more copolymerizable double bonds in the molecule or a mixture thereof (excluding those belonging to the above b)) 10 to 70 parts by weight The above a) b) and A heat-resistant resin composition containing c).

The present invention further comprises a heat-resistant resin laminate (FRP) characterized by impregnating a fibrous reinforcing material with this resin composition, and a fluororesin sheet containing the resin impregnated fibrous reinforcing material. It is a composite formed by laminating layers or a plurality of layers and curing and adhering them.

The novolac type epoxy methacrylate resin or novolac type epoxy acrylate resin (hereinafter referred to as novolac type epoxy (meth) acrylate resin) a) used in the present invention is a novolac type epoxy having two or more epoxy groups in the molecule. It can be easily produced by reacting a resin with methacrylic acid or acrylic acid (hereinafter referred to as (meth) acrylic acid) by a conventionally known method. For example, phenol novolac type epoxy (meth) acrylate is prepared by reacting a novolac type epoxy resin of phenol, bromophenol or cresol with an equimolar amount of (meth) acrylic acid in the presence of a polymerization inhibitor such as hydroquinone using triethylamine as a catalyst. Resin, brominated phenol novolac type epoxy (meth) acrylate resin or cresol novolac type epoxy (meth) acrylate resin is obtained. The above-mentioned novolac type epoxy resin is generally used as a mixture of compounds having several different molecular weights than a single molecular weight compound,
Also in the present invention, it is not limited by the degree of molecular weight distribution.

The polyfunctional (meth) acrylic acid ester b) used in the present invention is represented by the above-mentioned general formula (I), and is (meth) acrylic acid and a polyvalent compound having 2 to 20 carbon atoms and 2 to 6 valences. It is an ester with alcohol and is a saturated aliphatic polyfunctional (meth) acrylic acid ester having 2 to 6 intramolecular methacryloyl groups or acryloyl groups (hereinafter referred to as (meth) acryloyl groups). As an example (hereinafter, methacrylate or acrylate is referred to as (meth) acrylate) ethylene glycol, di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate, 1,3-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate,
Examples include dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, which may be used alone or in combination of two or more. To use.

The resin composition of the present invention can be obtained by adding a polyfunctional (meth) acrylic acid ester to the novolac type epoxy (meth) acrylate resin. The content of the polyfunctional (meth) acrylic acid ester is 20 to 80 parts by weight with respect to 100 parts by weight of the novolac type epoxy (meth) acrylate resin. If it is less than 20 parts by weight, the heat resistance and the resistance to organic solvents are not sufficiently improved. Further, if it exceeds 80 parts by weight, the air-drying property of the resin after curing at room temperature is deteriorated and the resin after curing becomes brittle, which is not preferable.

In the present invention, as a solvent for a novolac type epoxy resin or as a viscosity modifier for an epoxy (meth) acrylate, a monomer having at least one copolymerizable double bond in the molecule (the above-mentioned polyfunctional (meth ) Excluding those belonging to acrylic ester) c) can be added to obtain a resin composition. Examples thereof include vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, α-chlorostyrene and divinylbenzene, allyl ether or allyl ester compounds such as diallyl ether and diallyl phthalate, methyl (meth) acrylate,
Examples thereof include (meth) acrylic acid ester compounds such as ethyl (meth) acrylate and butyl (meth) acrylate, which may be used alone or in combination of two or more. The addition amount is novolac type epoxy (meth) acrylate resin 1
It is 10 to 70 parts by weight with respect to 00 parts by weight. If it is less than 10 parts by weight, the viscosity increases, and there is a problem in handling the resin at room temperature. If it exceeds 70 parts by weight, the effects of improving heat resistance and organic solvent resistance are suppressed, which is not preferable.

The novolac type epoxy (meth) acrylate used in the present invention has a heat resistance in the past, but it is said that the viscosity is too high and the workability is poor. By adding a copolymerizable monomer, Not only can the viscosity be adjusted and the resistance to organic solvents can be imparted, but the workability can be improved by lowering the viscosity of the resin composition.

To the resin composition of the present invention, a vinyl ester resin may be added with a conventional storage stabilizer such as copper naphthenate or the like or an additive such as wax or silicon. Further, at the time of use, a curing agent, a filler, a pigment, a release agent, a reinforcing agent, or the like can be added if necessary.

The resin composition of the present invention can be easily cured at room temperature by the same curing system as that of the conventional vinyl ester resin. That is, metallic soap is added to the resin composition used in the present invention and sufficiently stirred to uniformly disperse it. If necessary, acetoacetic acid ester and / or organic amine compound is added in a catalytic amount to accelerate curing and sufficiently stirred to uniformly disperse, and finally, organic peroxide is added and sufficiently stirred to homogenize. Disperse and cure.

The organic peroxide used as the curing agent is a ketone peroxide such as methyl ethyl ketone peroxide, a diacyl peroxide such as benzoyl peroxide, or a peroxy ester such as tertiary butyl perbenzoic acid which is usually used at room temperature. As long as it is a curing agent used for general vinyl ester resins, it is not particularly limited. As the metal soap, an organic cobalt salt having 2 to 18 carbon atoms is mainly used, but among them, cobalt octenoate and cobalt naphthenate are most frequently used from the viewpoint of compatibility with the resin. Organic amine compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyltoluidine, N, N-diethyltoluidine, N, N-bis (2-hydroxyethyl) aniline, N, N-. Aromatic amines such as bis (2-hydroxypropyl) toluidine, 1-methyl-2,3,4-trihydroquinone or tertiary alkyls such as triethylamine, tributylamine, N-methylmorpholine, N-methylpiperidine and triethylenediamine Amines are used.

Further, as a low temperature curing system having excellent heat resistance, a combination of acetoacetic acid ester peroxide, organic cobalt salt and acetoacetic acid ester (see Japanese Patent Publication No. 57-42084), purified methyl ethyl kent peroxide,
Tertiary alkyl peroxy ester, organic cobalt salt,
A combination of acetoacetic acid esters (see Japanese Patent Publication No. 57-4285) and the like are disclosed, and these can also be used. After the low temperature curing of the vinyl ester resin, after-curing is conventionally performed to make the curing more complete, but the resin composition of the present invention can also be subjected to after-curing at a temperature of 80 to 150 ° C.

In the resin laminate of the present invention, inorganic fibers such as glass, carbon, boron, alumina, and silicon carbide, which have been generally used for FRP as fiber-like reinforcing agents, polyester, polyethylene, polyamide, etc. These organic fibers can be used alone or in combination. Also F
It is used in various forms such as strands, chopped strands, chopped strand mats, surface mats, rovings, roving cloths, cloth tapes or swirl mats depending on the application and molding method of RP. The ratio of the resin composition to the fiber-like reinforcing material in the fiber-reinforced resin laminate of the present invention is 40 to 90% by weight, whereas the ratio of the reinforcing material is 60.
A range of 10 to 10% by weight is suitable. The amount of resin composition is 4
If it is less than 0% by weight, the adhesion as a reinforcing material will be insufficient and the heat resistance and corrosion resistance will be poor. 10% by weight of reinforcement
If it is less, the reinforcing effect will be small, and a laminate having sufficient strength for use will not be obtained.

The molding method may be a method known as a conventional FRP molding method. For example, any of hand lay-up method, spray-up method, filament winding method, centrifugal molding method, vacuum molding method and resin injection method may be used. Used.

The resin composition of the present invention is formed by directly impregnating and curing the resin on the fiber-reinforced surface of the one-side fiber-reinforced fluororesin sheet, or by further laminating a reinforcing material on it and impregnating and curing it to form a composite. can do. This composite is suitably used as a material such as a storage tank or a pipe for a highly corrosive liquid, which has a fluororesin sheet having excellent corrosion resistance as the liquid contact surface and is reinforced with the above FRP. When manufacturing a large capacity device, it is necessary to weld fluororesin sheets to each other, but the resin composition of the present invention is not damaged even at a considerably high welding temperature. If the device requires bending, it can be conformed to the shape by laminating a single layer of resin impregnated body on a fluororesin sheet. If structural strength is required, multiple layers of resin impregnated body can be laminated. Can meet that demand.

[0022]

The resin composition of the present invention is a prior application of JP-A-3-13.
As compared with the resin composition disclosed in No. 4028, by reducing the compounding ratio of the polyfunctional (meth) acrylic acid ester, the crosslink density is reduced and the rigidity is also reduced, so that the crack phenomenon after immersion in hot water can be avoided. It seems to be.

[0023]

Embodiments will be specifically described below with reference to embodiments. The parts in the examples are based on weight. Example 1 A phenol novolac type epoxy resin (“N-730” was added to a reactor equipped with a thermometer, a stirrer, a condenser and an air inlet tube.
-A "made by Dainippon Ink and epoxy equivalent 175) 330
Charged 0 parts and 893 parts of styrene monomer, 8 on the oil bath
Heat and stir to 0-90 ° C. After forming a uniform solution, 1
The temperature is raised to 10 ° C, and methacrylic acid 162 is added under an air stream.
A solution of 2 parts, 35 parts of triethylamine and 3 parts of P-tert-butylcatechol is added dropwise over about 1 hour.
The reaction was further continued at 110 ° C. for about 1 hour, and when the acid value reached 10, the reaction was terminated. 118 parts (epoxy acrylate resin containing 18 parts of styrene monomer) of 5850 parts of the obtained reaction liquid were sampled, and 36 parts of ethylene glycol dimethacrylate was added thereto to obtain a resin composition.
This composition was a transparent transparent liquid and had a viscosity of 230 CPS at 25 ° C. measured by a Brookfield viscometer.

Using this resin composition, cast products and laminates were produced by the following method. Two glass plates (200
mm × 150 mm × thickness 3 mm), a fluorine-based mold release spray (“Die-free A541” manufactured by Daikin Industries, Ltd.) is applied on the inner surface, and a spacer (thickness 10 mm) between the glass plates.
The silicone rubber frame) was placed and fixed with a clamp. To the gap of the glass plate, 0.5 part of cobalt naphthenate (cobalt content 6%) and 1 part of methyl ethyl ketone peroxide ("Permec N" manufactured by NOF Corporation) were added to 154 parts of the resin composition, respectively. After sufficiently stirring to make the mixture uniform, the mixture was poured and kept at room temperature for about 1 hour for exothermic curing. It was left to cool and then taken out to obtain a cast product. After gradually increasing the temperature of this cast product to 150 ° C and after-curing at 150 ° C for 1 hour, the heat distortion temperature (“HOT & V” manufactured by Toyo Seiki Co., Ltd.
Table 1 shows the measurement results of "SPT Tester" according to JIS6919).

In the same manner as described above, 0.5 part of cobalt naphthenate and 1 part of methyl ethyl ketone peroxide similar to those described above were added to 154 parts of the resin composition, and the resin was sufficiently stirred to prepare a glass surface mat ( Nitto Boseki's "MF30W") 1 ply, glass chopped strand mat (Nippon Glass Fiber's "REM4"
50 ") laminated with 3 plies and 1 ply of glass surface mat, 500 mm x 600 mm x 3 m thick
m FRP plate was manufactured. After exothermic curing, 1 ~ 100 ° C
After after-curing for 2 hours, a laminate having a size of 100 mm × 130 mm × thickness 3 mm was cut, the cut end was sealed with the same resin, and the test was performed. After immersing in chloroform at 50 ° C, visually observing its appearance and changing the bending strength according to JISK-7
The results of measurement by the method of 055 are shown in Table 1.

Example 2 A cresol novolac type epoxy resin (trade name "Epototo YDCN70" was used using the same apparatus as in Example 1.
1 ", epoxy equivalent 203) 609 parts and styrene monomer 445 parts were charged and melted at 80 to 90 ° C to 110 ° C.
The temperature was raised to 260 ° C., a solution of 260 parts of methacrylic acid, 20 parts of triethylamine and 1 part of hydroquinone was added dropwise over about 40 minutes, and the reaction was continued at 110 ° C. for 80 minutes to reach an acid value of 8.9. Then the reaction was completed. From 1335 parts of the obtained reaction liquid, 150 parts (styrene monomer 5
Epoxy acrylate resin containing 0 part) was collected and 40 parts of ethylene glycol dimethacrylate and 40 parts of trimethylolpropane trimethacrylate were added thereto to obtain a resin composition. Table 1 shows the results of measurement and production of castings and laminates using this resin composition in the same manner as in Example 1.

Example 3 118 parts of the reaction liquid in Example 1 was sampled, and 17 parts of a styrene monomer and 60 parts of trimethylolpropane trimethacrylate were added thereto to obtain a resin composition. Others are the same as in Example 1, and the measurement results are shown in Table 1.

Example 4, Comparative Examples 1 and 2 The procedure of Example 1 was repeated except for the composition and curing conditions as shown in Tables 1 and 2. The measurement results are shown in Tables 1 and 2.

Comparative Example 3 150 parts of the reaction liquid of Example 2 was sampled, and 40 parts of styrene monomer, 15 parts of ethylene glycol dimethacrylate and 15 parts of trimethylolpropane trimethacrylate were added and dissolved in the same manner as in Example 1. Was measured. The results are shown in Table 2.

[0030]

[Table 1]

[0031]

[Table 2]

Example 5, Comparative Example 4 On a stainless steel plate, a fluorine resin plate with a single-sided glass cloth (trade name: PFA plate ... made by Toray, tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin, 200 mm)
(Corner × thickness 3 mm) was fixed with a tape so that the glass cloth surface faced up. Next, to 100 parts of the resin composition of Example 1 and Comparative Example 1, 0.5 part of cobalt naphthenate (cobalt content 6%) and 1.5 parts of methyl ethyl ketone peroxide were mixed, and the glass cloth was well impregnated. Then defoam it and add chopped strand mat (4
50 g / m ² ) 4 plies were laminated to prepare a composite. This composite was after-cured at 50 ° C. for 1 hour and then divided into two.

Next, in order to re-bond the above-mentioned two-divided composite onto the stainless steel plate, the fluororesin surface is faced up and FR
Place it with the P side down and fix it by clamping. After V-cutting the contact surface between the composites, attach an air line mask and use a homogeneous fluororesin welding rod with a diameter of 3 mm for 280 to 280
Welding was performed while blowing hot air of 330 ° C. on the welded portion. After the welding was completed, after cooling to room temperature, the change in FRP on the back surface was examined. The resin composition of Example 1 did not change, but the resin composition of Comparative Example 1 changed its color to dark brown.

[0034]

INDUSTRIAL APPLICABILITY The resin composition of the present invention and the fiber-like reinforced laminate using the same have the following characteristics and are excellent in industrial applicability. (1) It has a high heat distortion temperature of around 200 ° C. (2) It has a high level of resistance to organic solvents that can withstand use at sufficiently high temperatures even with halogen-containing hydrocarbon solvents such as chloroform and trichlorethylene, which cannot be used with conventional unsaturated polyester resins and epoxy acrylates. .. (3) It has excellent hot water resistance and does not crack even after long-term immersion. (4) It can withstand thermal welding of fluororesin having a high softening point and can be used as a composite material. (5) The glass surface or glass chopped strand mat, the aramid fiber and the carbon fiber, which have been conventionally used in the FRP industry, have very good impregnability and can be used in the same manner as a general-purpose vinyl ester resin. Also FRP
It has a viscosity range suitable for processing, and not only ordinary processing operations but also molding operations having a small radius of curvature can be performed without lowering the heat resistance.

Claims (3)

[Claims] 1. A) 100 parts by weight of a novolac type epoxy (meth) acrylate resin, b) 20 to 80 parts by weight of a polyfunctional (meth) acrylic acid ester represented by the general formula (I) or a mixture thereof, ] (In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a polyhydric alcohol residue having 2 to 20 carbon atoms and a divalent to 6 valence.
Further, m represents an integer of 2 to 6, l represents an integer of 4 to 0, and 1 + m = 2 to 6. C) 10 to 70 parts by weight of a monomer having one or more copolymerizable double bonds in the molecule or a mixture thereof (excluding those belonging to the above b), a) b) and c). ) Is contained, The heat resistant resin composition characterized by the above-mentioned. 2. A heat-resistant fiber-reinforced resin laminate obtained by impregnating and hardening the resin composition according to claim 1 in a fiber-shaped reinforcing material. 3. A composite comprising a fluororesin sheet impregnated with the resin composition according to claim 1 in a single layer or a plurality of layers laminated and cured and adhered.