JPS59219363A - Resin composition having excellent adhesion - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent storage stability, curability and adhesion, consisting of a specified compd., an ethylenically or allylically unsaturated monomer, a catayst, a compd. contg. an oxirane ring and a hardener. CONSTITUTION:95.5-50wt% mixture obtd. by mixing at least one compd. (A) selected from among an unsaturated polyester, a reaction product obtd. from the reaction of a polyepoxide with an ethyleically unsaturated carboxylic acid in a molar ratio of 1:0.5-1.1 and a diallyl phthalate polymer, an ethylenically or allylically unsaturated monomer (B), e.g. styrene. copolymerizable with component A and a polymn. catalyst (C), e.g. benzoyl peroxide, in a mixing ratio of 0-100/0- 100/0.5-5, is mixed with 4.5-50wt% mixture obtd. by mixing a compd. (D) contg. an oxirane ring and a hardener (E), e.g. triethylene tetramine, for component D or a catalyst (F), e.g. BCl3, in a mixing ratio of 0-100/0-40/1-5.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition that is useful in storage stability, curability, and adhesion.

Radical resins such as unsaturated polyester resins, vinyl ester resins, and diallyl phthalate resins have been known as resin compositions with excellent curability, and have been widely used especially in the field of fiber reinforced plastics (FRP). It's here.

However, although the curability of 1stiffness resins is unclear, the properties of the cured product are generally inferior in toughness and have the disadvantages of insufficient adhesiveness.In order to improve the properties of 0stiffness resins, so far, After setting the terminal to a carboxyl group or a hydroxyl group, curing with an acid anhydride in combination with an epoxy resin, or a coexistence system of an unsaturated polyester resin, maleic anhydride, an epoxy resin, and an imidazole yarn hardening agent is used. Although these methods can produce certain effects, they have the drawback of slow reaction rate because they essentially involve the reaction between an acid anhydride and an ebokic group. When containing imidazole, there was a problem that storage stability was lacking.

The present inventors have arrived at the present invention as a result of intensive studies on resin compositions that have storage stability, curability, and adhesiveness.

That is, the gist of the present invention is that the reaction between at least one persimmon of polyepoxide (including unsaturated polyester) and at least -4;It of ethylenically unsaturated carboxylic acid;
substance (B), and diallylphthalate β polymer (C)
Fuha et al. At least one yuzu compound '1 Muku (I)
.

(1) and ethylenic or allylic vesicles that are common to each other.

(I), tjl) is a catalyst (111) that can be installed at the undercarriage entrance.

Compounds (IV) and (IV) containing at least one oxirane ring are cured by hardening agents (excluding Kihi Suido) (~
It is a 111 resin composition which has excellent curability and adhesion properties.

G″i (including unsaturated polyester used in the present invention),
Those produced by known methods using known raw materials can be used. That is, fumaric acid and maleic anhydride IW
71J Which unsaturated dicarboxylic acids and their acid anhydrides,
Saturated yubasic acids such as isophthalic anhydride, adipic acid, phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride IX, hexahydrophthalic anhydride, and their anhydrides, diethylene glycol, propylene glycol, neopentyl glycol, butanediol monohydrogen Examples include unsaturated polyesters obtained by a dehydration condensation reaction with a glycol component such as bisphenol A, 1-di(terhydroxypropoxyphenyl)propane, and the like.

(in the reaction product of polyepoxide and ethylenically unsaturated carboxylic acid) used as polyepoxide (1, but not particularly limited to, for example, diphenylolpropane,
Diphenyloethane, diphenylolmethane, diphenylol apolyglycidyl ethers, P-ami/
Produced by epoxidation of polyglycidyl ethers of polyvalent amines such as phenol, m-ami/phenol, Hiro, Hiro'-diami/diphenylmethane, and alicyclic compounds such as cyclohexene, Schifftetrapentadiene, and dicyclopentadiene. For epoxy and others 4, for poly(epoxy alkyl) ethers of aliphatic polyepoxy compounds such as J + 'l'-epoxy 6-methyl-cyclohexane carpones, ethylene glycol and glycerin, and for these polyepoxides. Examples include amine compounds, pre-reactions with r-tired anhydrides, and glycidyl esters of carboxylic or aliphatic carbons. Examples of ethylenically unsaturated carboxylic acids include methacrylic acid, acrylic acid, Examples include crotonic acid.Here, in the reaction of polyepoxide and ethylenically unsaturated carboxylic acid, the molar ratio of the epoxy group to the carboxylic acid is preferably i:o, s to l/.This reaction is performed using a known method. It can be carried out by the method [for example, the reaction described in Tokkosho, Dada 3/Dakuko Publication]. Diallyl phthalate β polymer C
) include β polymers such as diallyl phthalate and diallyl isophthalate.

Examples of the ethylenically or allylic unsaturated monomer (tJI) include styrene, vinyltoluene, styrene derivatives such as chlorostyrene, methacrylates such as methyl methacrylate, methyl acrylate, glycidyl acrylate, and glycidyl methacrylate, acrylates, diallylphthalate, and tristyrene. Examples include allyl esters such as allyl cyanurate and triallyl isocyanurate.

Examples of the polymerization catalyst K (ill) in (■)■ include peroxides active at medium to high temperatures such as benzoyl peroxide and t-butyl perbenzoate, and peroxides active at medium and high temperatures such as methyl ethyl ketone and cyclohexanone peroxide.

Examples of the compound (fV) containing at least one oxirane ring include the polyepoxides mentioned above, as well as monoepoxy compounds such as styrene oxide, butyl glycidyl ether, allyl glycidyl ether, and phenyl glycidyl ether.

(Curing agents M that can cure lVtl include diethylenetriamine, triethylenetetramine, 3.9-bis(
3-aminopropylene), da+&+10-tetraoxysubiro-(S,S]undecane, /, /, 3.J
Aliphatic polyamines such as tetramethyl-/, 3-amino/-propane, 3'M, m-xylylene diamine, aliphatic amines with aromatic moats such as tetrachloro-P-xylylene diamine, m-phenylene diamine, diaminodiphenyl Aromatic amines such as sulfone, Q, C-methylene dianiline, bis(kuami/-3 ethyl phenyl) methane,
Dicyandiamide 1.21A-xylenyl-biguanide, 0-tolylbiguanide, diphenylguanidine, guanicines such as di-0-1-lylguanidine, dihydrazides such as adipyl dihydrazide, azelainohydrazide, imidazoles such as coethylder methyl imidazole One example is knowledge. However, when using a K amine compound as the curing agent (V), it is necessary to use a peroxide with low activity toward γ amines, such as dicumyl peroxide, as the base initiator (111). (fV)
As a curing catalyst (Vl) capable of curing
I dichlorophenyl]3.3-dimethylurea, /-(
Examples include boron trifluoride amine complexes such as 'A ethoxyphenyl)-,7,J-dimethylurea, monoethylamine trifluoride, and boron trichloride amine complexes such as boron trichloride.

In the present invention, the blending ratio of (■) and ■l (1) satisfies general radical polymerization yarns, and the first is sufficient, but in general, (1) / (1) / (1) The ratio is θ~10θ10
~10θ/0. , t −j are excessive. Catalyst (L
If the ID is less than 05, a sufficient curing speed cannot be obtained, which is not unreasonable, but if it exceeds S, the curing will be rapid, which is not appropriate.

(IV) in the present invention, ("t17U, (V
The blending ratio of l) is sufficient as long as it satisfies the curing of general resins, but generally C1V)/(V)/
An appropriate ratio of ('Vl) is θ~100/θ~riθ/l~S. When the catalyst (Vl) is less than 1, a sufficient curing rate cannot be obtained, and when it exceeds S, the curing balance is lost and the curing agent remains unsuitable.

In the present invention, the ratio of the (I)/(II)/(III) mixture to the (Iv)/(V)/(Vl) mixture is 9! r
! ;/'Ajf-! ; θ/SO is appropriate and 6 o (
IV) / (V) / (vf) 'The footstool'm (Dti
If it is less than tffilxs%, sufficient N-contact property cannot be obtained, and 5
If it exceeds 0%, it is not possible to achieve substantial vC continuous curing, so one cycle is not appropriate.

The TL resin composition obtained by the present invention may optionally contain powdered fillers such as glass, silica, alumina, quartz, mica, calcium carbonate, barium sulfate, and clay.
It is also possible to use a mixture of pigments for each phase, colorants, and release agents such as zinc stearate and phosphate esters. In addition, inorganic fibers such as Karasu fibers, alumina fibers, silicon carbide constant fibers, boron fibers, and carbon fibers, as well as organic fibers such as polyester fibers and polyaramid fibers, are arranged in the form of chops, cloth, matte paper, etc. It can be used by applying it to the surface.

The present invention will be specifically explained below using Examples.

In addition, it represents the amount of 41 vehicles S in the example.

Example/Maleic anhydride 30 mol, diethylene glycol 108
Esterified at 23θC for 3.3 hours with a molar composition of 1'II~, then 30 mol of phthalic anhydride and 0 mol of hydroquinone.
．． 02t! PS 7J (1 and 3 at 190-230C
, Acid value 545 obtained by esterification for 1 hour / Unsaturated acid content / 98% unsaturated polyester / Diallyl 7 at θ0
Tallate monomark part, t-butyl perbenzoate 3
Miyako processing, SO'l:) on three rolls and kneading for 30 minutes to obtain composition ta). On the other hand, diglycidyl ether type epoxy resin '0's (
Epoxy equivalent 200) and dicyandiamide S, /-(
J, dacyclophenyl) -J, J-shichi/
Mix 3 urea and 30 minutes using a homomixer and mix composition (b). n TC6 (a) / (b) car b
The j ratio is 2j/7. ff.

,S-0/jS-0,'1 to/,2! Composition (c) (c-/
, c-co+cj+C-dan was obtained. The performance of this composition is shown in Table/.

Example Nidialyl phthalate prepolymer (OC1 iodine value 40 at softening point) 7! 1 part, diallylphtacy 1-monomerph, 2 parts, t-butylperbenzoate 3tfls were combined and kneaded for 30 minutes using three rolls, 2X, 11°1
M (+3) was obtained. Diglycidyl ether type epoxy compound to 10,000, bisphenol ++= (epoxy equivalent λ00) 100 units and +, lI'-diaminodiphenylsulfone q part /, S-0'C for 3 hours Uii
The tree obtained by combining l vehicles Htt /θ0 city and dicyandiamide, 5 cities, /- (terchlorophenyl) 3, 3 parts of 3-dimethylurea on three rolls! ;OC,, Knead for 30 minutes to obtain composition # (f).
S/ri 5.40/'10.75/, 25.9 g/ko on three rolls! ;OC, kneaded for 30 minutes to obtain the composition (g
) (g-/, g-co+gJ1g-hiro) was obtained.

The performance of this composition is shown in Table V.

Example 3 Diglycidyl ether type epoxy resin of bisphenol A (epoxy equivalent/90) 9! ; Methacrylic mJq in the part
Miyako, lithium chloride 07 Miyako, hydroquinone o, o
Add s H and heat reaction at 10θCT110 to obtain vinyl ester (E) F? with acid value of 30. V-tail. A resin composition (1) is prepared by mixing vinyl ester (h) A Ohls, styrene θ parts, and 2S parts of t-butyl perbenzoate.
I got it. Bisphenol A diglycidyl ether type epoxy resin (epoxy equivalent g/90) 'IQ capital, θ-cresol/borac diglycidyl ether type epoxy resin (epoxy equivalent weight 2-〇) AO capital, N, N, O-triglycidyl m-Ami/Phenol (Epoxy/Yo)
ioH, 5 parts of dicyandiamide, and 3 parts of l-(terchlorophenyl)-3,3-dimethylurea on a triple roll.
A persimmon 11F+composition (j) was obtained by kneading for 0C3θ minutes. (
i) / (j) volume ratio to 577s, AO1hiro θ, 7 /
2! ;, qg/yu to give the composition (k) (k-/
, ni-yu, ni-3, ni-da]. The performance of this composition is shown in Table 3.

Actual h (l≠ W ffTlm Example 3 Vinyl ester Lh in VC)
70 W6, 30 parts of glycidyl methacrylate, and tertiary butyl barpenzoate were mixed, and then dicyandiamide θ, / -(II-chlorophenyl), 3,3-dimethylurea θgsE were mixed to prepare the other side composition. 9J Akira) was obtained. This composition had a storage stability of 3θ days or more at -3C, the gel time of /HiroC was /+2 minutes, and the heat distortion temperature was 1HiroOC. 3 V instead of Q maleic anhydride @/part, /-(3,3-dichlorophenyl)
Composition (d) was obtained in the same manner except that 3 parts of coetiludamethylimidazole was used in place of 1 part of -,3,3-dimethylurea J. This composition table was tested in accordance with ASTM-D-/θθyu until the gel time of OC under 2sc'a became S of 11"↓iσ. 25
The shear strength of C is shown. The same shall apply to the following Tables. Relationship with the case of the person making the amendment Applicant: 2-3-19 Kyobashi, Chuo-ku, Tokyo (603) Akio Kawasaki, President and CEO of Mitsubishi Rayon Co., Ltd. 4, Agent: 3-19 Kyobashi 2-chome, Chuo-ku, Tokyo 7. Contents of correction Table 1 on page 14 will be corrected as shown in the attached sheet.

*2 Fit 6 After curing at a curing temperature of 145℃, post-cure at 150℃ for 2 hours.

” 2. Correct Table 2 on page 15 as follows.

Rice 1 After curing at a curing temperature of 145°C, further post-curing at 160°C for 2 hours. ”a
15 Correct table 6 as follows.

N1 After curing at a curing temperature of 145°C, further post-curing at 160°C for 2 hours.

Table 4 on page 4 and 16 is corrected as follows.

111 After curing at a curing temperature of 145°C, further cure at 160°C x 2
harden after hours.

”

Claims (1)

[Claims] At least one compound (■n. I) , (1, [) to chassis 18i] capable catalyst CIJ
I). Compound ■ containing at least one oxirane ring. and ([\l)? Curable curing agent (excluding acid anhydride)
Resin composition with curability and adhesive properties [4%,