JPS5978224A - Resin composition - Google Patents

Abstract

PURPOSE:A new resin composition having high strength and high impact resistance and being useful as a casting material or FRP material used in a hand lay-up process, prepared by blending a vinyl ester resin with a low-reactivity unsaturated polyester having a specified MW per double bond. CONSTITUTION:The desired resin composition is prepared by blending (A) an unsaturated ester prepared by reacting an epoxy resin with an unsaturated monobasic acid and, optionally, an acid of a higher dasicity, (B) an unsaturated polyester having an MW, per double bond, of 400-21,000 (e.g., a dicyclopentadiene-modified unsaturated polyester of a softening point <=70 deg.C) and optionally, (C) a polymerizable monomer (e.g., p-methylstyrene). A preferable example of the proportion of the components in the above composition is as follows: 10- 90pts.wt. unsaturated ester, 0.1-50pts.wt. unsaturated polyester, and 1-150pts.wt. polymerizable monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high-strength and impact-resistant resin composition, which can be used as a casting material for reed, hand lay-up method, preform mated metal die molding method, sheet molding compound method, etc. The present invention relates to a novel resin composition 11 which is extremely useful as a filler for FRP.

A resin made by reacting an epoxy resin with an unsaturated basic acid such as methacrylic acid and dissolving an unsaturated ester in a polymerizable monomer such as styrene resin is generally called vinyl ester resin and is widely used as a material for casting, FRP, etc. used in However, although this vinyl ester resin has relatively high strength, it has the drawback of poor impact resistance. For this reason, in the case of FRP helmets, FRP for automobile parts, etc., the thickness of the molded product must be increased, making it extremely difficult to reduce the weight.

The present inventors conducted intensive studies to develop a resin composition with high strength and high impact resistance, and found that a vinyl ester resin was combined with a low-reactivity unsaturated polyester having a molecular weight of 400 to 21,000 between double bonds. It was discovered that a resin composition with extremely high strength and high impact resistance could be obtained by blending the following.

This led to the present invention.

That is, the present invention.

Unsaturated ester 7 (Bl double bond per fi(7) molecule i; 7400-2
1,000 unsaturated polyester and optionally (C) a polymerizable monomer.

The present invention will be explained in detail below.

As the epoxy resin used for the unsaturated ester of the present invention, novolac epoxy resin, bisphenol epoxy resin, alicyclic epoxy resin, etc. are used alone or in combination of two or more.

Commercially available novolac epoxy resins include E, N431, D, E, manufactured by Dow Chemical Company,
N438. Epicoat 152 manufactured by Shell Chemical Co., Ltd. Epicote 154. There is EPN1138 manufactured by Ciba.

Also, as a bisphenol epoxy resin.

Commercially available low-molecular-weight epoxy resins obtained using bisphenol as a reaction material include Epicoat 828° and Epicoat 1001, manufactured by L Kagaku Co., Ltd. Epicote 1004. Ciba Acyldite 6094. Examples include Araldite 6097.

Examples of alicyclic epoxy resins include vinylcyclohexene dioxide (trade name Chissonox 206), synchlopentadiene dioxide (Chissonox 207X),
3.4-Epoxy-6-methylcyclohexylmethyl 3
．． Examples include 4-epoxy-6-methylcyclohexane carbonate (Chissonox 201).

In addition, epoxy resin derivatives such as Epototo YDB-340 and Evototo YDB-400 manufactured by Tobu Kasei Co., Ltd. can also be used.

Examples of unsaturated dibasic acids to be reacted with epoxy resin include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid,
) ricin o[:5,2,1.0”:]-4-decene-8
Alternatively, a partially esterified carboxylic acid containing 9 residues and an unsaturated dibasic acid residue as constituent elements can be used.

Examples of partially esterified carboxylic acids include 8- or 9-hydroxytricyclodecene-4-[5,2,1,0'')
An unsaturated dibasic acid monomer obtained by heating 1.00 to 1.20 mol and 1 mol of an unsaturated dibasic acid such as maleic anhydride, itaconic acid, or citraconic acid at 70 to 150°C under an inert gas stream. There is an ester.

Tricyclodecadiene-4,8-(5,su1,0”:1
An unsaturated dibasic acid monoester obtained by adding an unsaturated dibasic acid such as maleic acid, fumaric acid, or itaconic acid to the ester in the presence of a catalyst such as sulfuric acid or Lewis acid can also be used.

Polybasic acids that are reacted with epoxy resin as necessary include:
Unsaturated dibasic acids such as maleic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid.

There are saturated polybasic acids such as noadibic acid and pyrometic acid. These can be used alone or in a mixture of two or more. When a polybasic acid is reacted with an epoxy resin, it becomes possible to attach an acid group to the side chain of an unsaturated ester, and this acid group reacts with a thickener such as magnesium oxide, resulting in a sheet molding compound (SMC). It is particularly useful in law.

The temperature of the epoxy resin and the unsaturated basic acid and polybasic acid to be reacted as necessary is 60-150°C.

Preferably, it is heated to 70 to 130°C to react to form an unsaturated ester. Approximately 1 equivalent of the unsaturated basic acid is used per 1 equivalent of the epoxy resin.

When performing a complete reaction with a polybasic acid, 1.03 amounts of the epoxy resin and 1.0 equivalent or less of the unsaturated basic acid are added in advance.9 Usually, 0
．． It is preferable to react an amount of 95 to 0.70 M, and react 1.0 mole of polybasic acid with respect to 1.0 equivalent of unreacted epoxy group.

The acid value of the unsaturated ester produced is 50 or less.

It is preferably 20 or less. In order to prevent gelation due to polymerization during the reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, ditertiary butylcatechol, or hydroquinone monomethyl ether.

In addition, during this esterification reaction, ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, tertiary amines such as triethylamine and dimethylaniline, ferric chloride, lithium hydroxide, lithium chloride, and tin chloride are used. Esterification catalysts can also be used to shorten the reaction time.

Next, an unsaturated polyester having a molecular weight per double bond of 400=21,000 will be explained. The materials used for the unsaturated polyester include acids and alcohols that are commonly used for unsaturated polyesters. Examples of acids include unsaturated dibasic acids such as maleic anhydride and fumaric acid, isophthalic acid, terephthalic acid, orthophthalic acid, and adipic acid.

Saturated dibasic acids such as tetrachlorophthalic anhydride are used.

Alcohol toshiteha, ethylene glycol.

7°ropylene glycol, neopentyl glycol,
Dibromoneopentyl glycol, cyglobylene glycol, diethylene glycol, bis[hala(hydroxy-n-propoxy)phenyl]cropane, trimethylolpropane.

Polyhydric alcohols such as polyfujiene glycol are used. Linseed oil, soybean oil as needed.

These transesterified oils, fatty acids, etc. are used.

Unsaturated polyesters may be modified with dicyclopentadiene, and methods for modification include (1) a one-step synthesis method in which acid, hyalcohol, and dicyclopentadiene are simultaneously charged and condensed, and modified at the same time; (2) Add acid and alcohol to condense.

There is a two-step synthesis method in which dicyclopentadiene is added and modified during the process, but either method is possible. The amount of dicyclopentadiene used is not particularly limited, but the acid component 1
．． For 0 mole, dicyclopentadiene 0.05-0
．． It is preferable to use it in the range of 40 molar. If the amount of dicyclopenta or diene added is less than 0.05 mol, the compatibility with the vinyl ester resin will decrease;
If the amount exceeds 0 mol, impact resistance tends to decrease. The reaction temperature when modifying unsaturated polyester with dicyclopentadiene is preferably in the range of 150 to 230°C.

The molecular weight of the double bond is calculated as follows, for example. In the case of an unsaturated polyester obtained from maleic anhydride and propylene glycol, the molecular weight of maleic anhydride is 98. The molecular weight of propylene glycol is 76, and the total molecular weight of 9 is 174. Subtracting the molecular weight of water lost by condensation, 18, from this gives 156, which is the molecular weight per double bond. In the case of an unsaturated polyester obtained from 0.3 mol of maleic anhydride, 0.7 mol of phthalic anhydride and 1.0 mol of hyclobylene glycol, similarly (98X0.3+148X0
．． 7+7゛6X1.0-18)÷0.3=636.7, that is, 636.7 is calculated as the molecular weight of the double bond. The molecular weight of the double bond is not the calculated molecular weight,
It differs from the actual molecular weight by e. Furthermore, in calculations, the glycol excess rate is not taken into account, and calculations are made assuming equimolar amounts of acid and glycol. When unsaturated polyester is modified with dicyclopentadiene, dicyclopentadiene is blended so that part of the dicyclopentadiene is added to the double bonds of the unsaturated polyester. By way of denaturing.

The proportion of dicyclopentadiene added to the double bonds of the unsaturated polyester varies, but is determined by analyzing the NMR (nuclear magnetic resonance) spectrum of the unsaturated polyester after modification.

The molecular weight of the double bonds in the unsaturated polyester is 550 to 4,400, which provides a good balance between strength and impact resistance.

Furthermore, in order to improve the impact resistance of the resin composition of the present invention, it is particularly effective when the unsaturated polyester is a soft type. Therefore, the softening point of unsaturated polyester (according to JIS K 2531, softening point by ring and ball method) is 7.
The temperature is preferably 0°C or lower.

Polymerizable monomers used as necessary include styrene, divinylbenzene, methylstyrene, vinyl acetate,
Methyl methacrylate, ethyl acrylate, ethylene glycol dimethacrylate, etc. are used, but styrene is mainly used. Further, it is preferable to use p-methylstyrene because it improves heat resistance. In the present invention, it is not always necessary to use a polymerizable monomer.

The proportions of unsaturated ester, unsaturated polyester, and polymerizable monomer are not particularly limited, but from the viewpoint of balance of strength and impact resistance, 10 to 90 parts by weight of unsaturated ester and 0.1 to 50 parts by weight of unsaturated polyester. Partially polymerizable monomer 1
The range of 50 parts by weight is preferable, and the unsaturated ester is 50 to 9 parts by weight.
0 parts by weight, 0.5-40 parts of unsaturated polyester]ii part.

A range of 5 to 100 parts by weight of the polymerizable monomer is more preferred. The range with the best balance between strength and impact resistance is 60 to 90 parts by weight of unsaturated ester and 0.5 to 20 parts by weight of unsaturated polyester.

The amount of polymerizable monomer is 10 to 50 parts by weight.

The resin composition of the present invention contains an organic peroxide for curing, an accelerator for curing, 9 a polymerization inhibitor, if necessary.

It may also contain fillers, reinforcing materials, mold release agents, colorants, thickeners, and the like.

Examples of the curing organic peroxide include t-butyl peroxybenzoate, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, and methyl ethyl ketone peroxide.

Cobalt octenoate is used as a curing accelerator.

Examples include metal compounds such as cobalt naphthenate, potassium octenoate, and manganese naphthenate, and tertiary amines such as dimethylaniline and diethylaniline.

Examples of polymerization inhibitors include hydroquinone, parabenzoquinone, catechol, and 2,5-cyenylparabenzoquinone.

Calcium carbonate and clay are used as fillers.

Examples include barium sulfate and aluminum hydroxide.

Glass fiber and vinylon fiber are used as reinforcement materials.

Various processed materials such as a roving made of carbon fibers or other fibers, short fibers, knitted fabrics, and single thread braids may be used.

Examples of mold release agents include zinc stearate and calcium stearate. As the colorant, all of the inorganic and organic colorants currently used for coloring unsaturated polyester resins can be used.

As the thickener, metal oxides such as magnesia oxide and calcium oxide, metal hydroxides such as magnesium hydroxide, organic thickeners using diisocyanates such as diphenylmethane diisocyanate, and combinations thereof can be used.

In addition, heat-resistant polymers such as polystyrene, polyvinyl acetate, polymethyl methacrylate, saturated polyester, and phenol are also added as required.

Thermosetting polymers such as epoxy and melamine may also be used in combination, antimony trioxide, hexabrompe7zene,
All flame retardants such as chlorinated paraffins may be used.

The resin composition of the present invention can be applied not only to normal temperature and normal pressure molding methods such as hand layag and spray up, but also to resin injection molding methods, preform mated metal die molding methods, sheet molding compound methods, and bulk molding compound methods. The range of applications is extremely wide.

Example 1 Methacrylic acid 172. OS' (2.0 mol), bisphenol epokine resin Epicor) 828 (Shell Chemical Co., Ltd., epoxy equivalent 189) 151.2y-(0.40 mol), Epicort 1001 (Shell Chemical Co., Ltd., epoxy equivalent 475) 570.0y -(0.60 mol), hydroquinone 0.40? A resin (VE-1) was obtained by mixing 70 parts of an unsaturated ester with an acid value of 9 obtained by heating 0.50 y-trimethylbenzylammonium chloride at 120° C. for 7 hours and 30 parts of styrene.

'Propylene glycol 418i (5.5 mol).

Diethylene glycol 5309' (5,0 mol), adipic acid 146i (1,0 mol), 7-maric acid 348% (3
, 0 mol), 7-talic anhydride 888y-(6,0 mol) was heated in a nitrogen stream')'r from 150°C to 210'CJC' for 5 hours, and then synthesized at 210°C for 10 hours. 70 parts of unsaturated polyester with a value of 30 and 0 parts of hydroquinone
．． The resin was mixed with 30 parts of styrene containing 0.005 parts and dissolved to obtain a resin (UP-1). The molecular weight of the double bond of this unsaturated polyester is 680, and the softening point by the ring and ball method is 5.
The temperature was below 0°C.

FRP with a glass content of 60% was produced using VE-1 and UP-1 according to the formulation shown in Table 1. The strength is shown in Table 1, and it shows excellent strength characteristics.

%, excellent strength properties can be obtained at high temperatures (60°C). Also, due to its low modulus of elasticity, it had excellent impact resistance. Figure 1 shows the load-deformation curves when measuring the bending strength of the obtained FRP.
is the curve at 60°C. As a result, the obtained F
It is shown that the elongation at break of RP is extremely low.

Example 2 Propylene glycol 41sy (5.5 mol).

Diethylene glycol 530g (5,0 mol), adipic acid 146p (1,0 mol), fumaric acid 116,%
(1.0 mol), phthalic anhydride 11847 (8.0 mol) was heated from 150°C to 210°C in 5 hours under a nitrogen stream, and then synthesized at 210°C for 10 hours, with an acid value of 32.
70 parts of unsaturated polyester and 0.00 parts of hydroquinone
5 parts of styrene, and dissolve the resin (
UP-2) was obtained.

The molecular weight of the double bond of this unsaturated polyester is 21
40. The softening point determined by the ring and ball method was 50°C or less.

When VE-1 and UP-2 were used to prepare F]%P with a glass content of 60% according to the formulation shown in Table 1, it showed excellent strength and high elongation. Furthermore, the strength when heated (60° C.) and the elongation at break were also excellent.

Comparative Example 1 PR, P with a glass content of 60% was produced using the VE-1 obtained in Example 1 with the formulation shown in Table 1. It showed low elongation, low strength at heat, and poor impact resistance. They were also inferior in gender. FIG. 1 shows a load-deformation curve when measuring the bending strength of the obtained FRP.

2 is a curve at 23°C, 4 is a curve at 60°C, Example 1
It is shown that the elongation at break is inferior to that of FRP.

Comparative example 2 Propylene glycol 790P (10,5 mol).

Maleic anhydride 490P (5.0 mol) and phthalic anhydride 740y (5.0 mol) were heated from 150°C to 210°C in 5 hours under a nitrogen stream, and then synthesized at 210°C for 7 hours. A resin (UP-3) was obtained by mixing 70 parts of unsaturated polyester with an acid value of 35 and 30 parts of tr styrene containing hydroquinone o and oos and dissolving it. The molecular weight of the double bond of this unsaturated polyester is 362. The softening point determined by the ring and ball method was 72°C.

Using VE-1 and UP-3 obtained in Example 1, Table 1
When FRP with a glass content of 60% was produced using the formulation shown in Figure 1, the strength was low, the elongation was extremely poor, and the impact resistance was also poor.

Example 3 Methacrylic acid 86i (1.0 mol), novolac epoxy resin, E, N, 438 (manufactured by Dow Chemical Company,
Epoxy equivalent 179) 179y-(1 epoxy a lid),
Resin (VE-2) was prepared by mixing 70 parts of an unsaturated oroester with an acid value of 14 obtained by heating at 90°C for 7 hours and 30 parts of styrene. I got it.

Using VE-2 and UP-1 obtained in Example 1, Table 2
A resin cast product was obtained using the formulation shown below. The characteristics are shown in Table 2,
It showed excellent strength and high elongation.

The heat distortion temperature also showed a high value.

Comparative Example 3 Using VE-2 obtained in Example 3, a resin cast product was obtained with the formulation shown in Table 2. The properties are shown in Table 2, and the elongation was low and the heat distortion temperature was also low.

Table 2 Formulation and characteristics Curing conditions 80°C for 30 minutes, then 120°C for 3 hours Example 4 Methacrylic acid 155. (1(), 8 mol), bisphenol epoxy resin Ebiko) 828 (Shell Chemical Exhibition, epoxy equivalent 189) 113.4P (0,30 mol)
, Epicote 1001 (Shell Chemical Exhibition, epoxy equivalent weight 4
75) 570.01i' (0.60 mol), hydroquinone 0.409- and trimethylbenzylammonium chloride 0.50Pe When heated at 120°C for 5 hours, the acid value decreased to 8.

To this was added 23.1' (0.20 mol) of maleic acid.

A resin (VE-4) was obtained.

490 parts of VE, 210 parts of 7tUP obtained in Example 2, 0.01 part of rosebenzoquinone, 1.0 part of tanyabutylperbenzoate, 120 parts of calcium carbonate, and 4.0 parts of zinc stearate were mixed well.

A compound was prepared. Add 1.0 part of magnesium oxide (+20) to this compound and mix quickly.
Glass chopped strand mat placed on polyethylene film (FEM-4 manufactured by Fuji Fiberglass Co., Ltd.)
50) SMC with a glass content of 28 inches was prepared by coating on 64 parts and thoroughly impregnating it. SMC is 48 at 40℃
After some time, the adhesiveness with the film disappeared.

The 5MCe molding temperature was 140°C and the molding time was 3 minutes.

Molding was performed at a molding pressure of 50 Ky/cm2. The molded product has a bending strength of 22.0 to 5+/mm” and a bending modulus of 980K.
f/m”, tensile strength 9.2 Ky/lrtm2.
Charpy impact strength 51.9 to 9cm/crrr'
It showed excellent strength.

Example 5 Acrylic acid 144.1 t (2.0 mol), bisphenol evoquin resin Epicor) 828 (Shell Chemical Exhibition, epoxy equivalent 189) 189.0y- (0.50 mol), Epicor) 1001 (Shell Chemical Exhibition) , epoxy equivalent weight 475) 475.0i (0,50 mol).

Hydroquinone 0.4? A resin (VE-5) was obtained by mixing 70 parts of an unsaturated ester having an acid value of 10 obtained by heating 0.5y- of trimethylbenzylammonium chloride at 110° C. for 7 hours and 30 parts of p-methylstyrene.

580 parts of VE-2, 220 parts of UP-2 obtained in Example 2, and 1.0 part of benzoin methyl ether were thoroughly mixed for 7 minutes. This resin was applied to a thickness of 100 μm on an iron plate and cured by irradiation with ultraviolet light (80 W/crn high-pressure mercury lamp, Toshiba Denzai H2000L/6 lamp, distance 30 Cn1, 1 minute). Low odor during curing, Erichsen extrusion 7IIO11 or higher, Dupont impact 50crI
A good coating film of t or more was obtained.

[Brief explanation of drawings]

Figure 1 shows 2 of F'RP obtained in Example 1 and Comparative Example 1.
It is a figure which shows the load-deformation curve at the time of bending strength measurement at 3 degreeC and 60 degreeC. Explanation of symbols 1...FRP of Example 10 (23°C) 2...FRP of Comparative Example 1 (23°C) 3...FR, P of Example x (6 parts°C) 4... Comparative Example 1 FRP (6 parts ℃) Y 1 arrogant town (scolding

Claims (1)

[Scope of Claims] 1,'(A) Unsaturated/phenethyl (I31, molecular weight of double bond 400 ~21,0
00 unsaturated polyester and optionally (C1 polymerizable monomer). 2 10 to 90 parts by weight of unsaturated ester and 0.1 to 50 parts by weight of unsaturated polyester Polymerizable monomer ~15
The resin composition according to claim 1, which contains 0 parts by weight. 3. 50 to 90 parts by weight of unsaturated ester, 0.5 to 40 parts by weight of unsaturated polyester Polymerizable monomer to 10 parts by weight
The resin composition according to claim 1, which contains 0 parts by weight. 4. 60 to 90 parts by weight of unsaturated ester, 0.5 to 20 parts by weight of unsaturated polyester, parts by weight of polymerizable monomers 0 to 5
The resin composition according to claim 1, which contains 0 parts by weight. 5. The unsaturated polyester has a double bond and a molecular weight of 55.
The resin composition according to claim 1, which is an unsaturated polyester having a molecular weight of 0 to 4,400. 6. The resin composition according to claim 1, wherein the unsaturated polyester is an unsaturated polyester obtained by modification with dicyclopentadiene. 7. The resin composition according to claim 1, wherein the unsaturated polyester has a softening point of 70° C. or lower. 8. The resin composition according to claim 1, wherein the polymerizable monomer is p-methylstyrene.