JPH0797415A - High-hardness resin composition and integral molding thereof with organopolysiloxane composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a warpage-free and sink-free product even when cured under ordinary pressure conditions by mixing a specified polyfunctional compound with a free-radical initiator, a filler and a monohydrogen-phosphoric ester or a dihydrogenphosphoric ester. CONSTITUTION:The title composition is prepared by mixing a polyfunctional compound represented by the formula: R2C=CR-Y (wherein R is H or a monovalent hydrocarbon group; and Y is a molecular chain comprising an organic atomic chain or a silocane chain) and having at least two unsaturated groups each having an aryl group adjoining to the double bond with a free-radical initiator, a filler and 0.01-20 pts.wt. monohydrogen-phosphoric ester and/or dihydrogenphosphoric ester. A molding made by integrally molding the above composition with an organopolysiloxane composition containing a free-radical initiator by crosslinking them by heating has very tight inseparable adhesion between the both because of the crosslinking.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a high-hardness resin composition, particularly a high-hardness resin composition which does not cause warping or sinking even when cured without pressure, and an organopolysiloxane composition thereof. And a molded body using the composition of the present invention, in which a high-hardness portion and an elastic portion are mixed and are applied to various molded bodies that are required to be strongly bonded. However, for example, so that the bottom portion is not damaged by the impact of placement, only the bottom portion is an elastic body, a vase with a liquid-containing concave portion having a high hardness resin composition, a beverage container, An example is a cover member for a push button switch used for input operation of a coaster, an ashtray, a remote controller, a calculator, a telephone, an OA device, and the like, and particularly a cover member for a push button switch having a hard portion having no stickiness on a key top portion. That.

[0002]

2. Description of the Related Art Various products are known from the past in which a high-hardness resin composition having rigidity and an organopolysiloxane composition in the form of a rubber-like elastic material are joined together. Most of them are bonded with an adhesive or a pressure sensitive adhesive, or they are bonded with a physical means such as fitting or bolting, so that it is difficult to handle them as an integrally molded product.

Therefore, the inventors of the present invention have previously proposed a cover member for a push button switch in which a high hardness resin composition for a key top is integrally formed with a thin movable portion, a base portion, a contact portion and the like made of a rubber-like elastic body. (See Japanese Patent Laid-Open No. 4-355004). Explaining this in detail, a high-hardness resin composition comprising a compound having a plurality of functional groups capable of radical resonance represented by a methacryloyl group, an allyl group and a mesalyl group and an organic peroxide (here, a high-hardness resin composition Is cured I
A liquid or paste in which RHD is 90 ° or more. ) Is filled in the dug portion for forming the key top portion of the die, and synthetic rubber containing organic peroxide is filled in the dug portion for forming the thin-walled movable portion and the base portion of the die, and pressurization and heating are performed. This is a cover material for pushbutton switches that is integrally molded by co-crosslinking in a metal mold. It has a key top part with excellent hard finger feel and a soft pressing feeling and the responsiveness of deformation restoration due to pressing release. The agile, thin-walled moving part is integrated. Further, the method of manufacturing the cover member for a push button switch disclosed in JP-A-5-67410 proposes the timing of integral molding of the high hardness resin composition and the synthetic rubber proposed in JP-A-4-355004. Explaining this in detail, the dug portion for forming the key top portion of the heated die is filled with a high-hardness resin containing an organic peroxide. At this time, the high-hardness resin loses fluidity. If the synthetic rubber containing organic oxide is filled into the thin-walled movable part and the digging part forming the base part and co-crosslinking is integrally molded in the mold after the state, the resilience of deformation restoration becomes even more agile. In addition, the invention is that the fatigue resistance against deformation is also increased. In addition, regarding this, in Japanese Patent Application No. 5-92805, a high hardness resin composition is provided, in particular, a key top part made of a high hardness silicone resin having a diphenyl skeleton or a methylphenyl skeleton, a thin movable part made of silicone rubber, a base part, A cover member for a push button switch, which is integrally formed with the contact portion by co-crosslinking, is proposed.

[0004]

However, as a result of further study of a cover member for a push button switch having this high hardness resin composition as a key top portion, the main raw material of this high hardness resin composition is widely used. Since it is a raw material, it has the advantage that the raw material is inexpensive, but if this conventional high hardness resin composition is filled in the dug portion for forming the key top portion of the mold, the resin shrinks as the resin cures. Therefore, when the key top portion is cured without pressure, the high-hardness resin composition undergoes shrinkage due to the curing and shrinkage, which is represented by warpage and sink marks. The thin movable part on the key top part formed by
When the synthetic rubber containing organic peroxide is filled into the dug portion for forming each part of the mold to pressurize and heat to integrate the base portion, the key top portion has warp or sink mark. Therefore, it has been found that the synthetic rubber wraps around to the key top portion, resulting in a disadvantageous appearance of the target cover member for the push button switch and poor dimensional accuracy.

The key top portion is made of a high hardness silicone resin, and the warp or sink mark is formed on the cover member for the push button switch which is integrally formed with the thin movable portion made of silicone rubber, the base portion and the contact portion. Although it does not occur, it is expensive because the raw material is special, and this has the disadvantage that the key top part may crack if it is handled roughly because the impact resistance is rather weak. It turned out that

[0006]

The present invention relates to a high-hardness resin composition which solves the above disadvantages and problems, and an integrally molded product of the high-hardness resin composition and an organopolysiloxane composition. Is represented by the general formula R ² C = CR-Y (where R is a hydrogen atom or a monovalent hydrocarbon, and Y is a compound main chain consisting of an organic atom chain and / or a siloxane chain), and the carbon atom adjacent to the double bond is A polyfunctional compound having at least one hydrogen atom in an atom or two or more unsaturated groups having an aryl group adjacent to a double bond, a radical initiator and a filler, and a monohydrogen phosphate ester and / or The present invention is characterized by containing 0.01 to 20 parts by weight of a dihydrogen phosphate ester. The integrally molded product of the high hardness resin composition and the organopolysiloxane composition is the high hardness resin composition. And it is characterized in that obtained by co-crosslinking integrally molded with organopolysiloxane containing a radical initiator.

That is, the present inventors have conducted various studies to develop a high-hardness resin composition that does not cause warpage or sink even when it is cured under no pressure. As a result, this high-hardness resin is generally used. Formula (1) R ² C = CR-Y (wherein R is a hydrogen atom or a monovalent hydrocarbon group, Y is a compound main chain),
A polyfunctional compound having at least one hydrogen atom on a carbon atom adjacent to a double bond or having two or more unsaturated groups adjacent to an aryl group on a double bond, or a general formula (2) CH ₂ = CH A monofunctional compound having one unsaturated group represented by —CH ₂ —Y and / or one unsaturated group having an aryl group adjacent to the double bond represented by the general formula (3) CH ₂ ═CH—Y A high-hardness resin molded product can be obtained by heating and curing a monofunctional compound having a radical initiator and a filler added thereto. However, this will cause warpage and sink marks. It was found that the addition of an ester and / or a dihydrogen phosphate ester gives a high-hardness resin molded body free from warpage and sink marks, and this high-hardness resin composition is used together with an organopolysiloxane composition containing a radical initiator. heating , Curing these Verify that the integrated co-crosslinking, the amount of each component, and completed the present invention by studying on such processing conditions.
This will be described in more detail below.

[0008]

The polyfunctional compound which is one of the constituents of the high hardness resin composition of the present invention is represented by the general formula (1) R ² C = CR-Y, where R is a hydrogen atom or a monovalent hydrocarbon group, Y
Is a compound main chain composed of an organic atom chain and / or a siloxane chain, and has at least one hydrogen atom on a carbon atom adjacent to the double bond carbon, or an unsaturated group adjacent to an aryl group on the double bond. It has two or more groups, or three or more groups, and includes ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Ethylene glycol # 200 dimethacrylate, 1,3-
Butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, bisphenol A dimethacrylate, EO modified phosphate dimethacrylate, dicyclopentynyl dimethacrylate, glycidol dimethacrylate. Methacrylate, allylated cyclohexanyl diacrylate, diallyl phthalate,
Diallyl carbonate, diethylene glycol bisallyl dicarbonate, pentaerythrite diallyl ether, triallyl trimellitate, 1,5-hexadiene, 1,4-hexadiene, 6-methyl-1,5-heptadiene, 11-ethyl-1,11- Examples thereof include tridecadiene and the like, and polyfunctional monomers such as tris (methacryloxyethyl) isocyanurate, trimethylolpropane trimethacrylate, triallyl isocyanurate, trimesaryl isocyanurate, methacryl urethane modified at both ends, and modified 1,2-polybutadiene.

Furthermore,

[0010]

[Chemical 1]

[0011]

[Chemical 2]

[0012]

[Chemical 3]

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

[0020]

[Chemical 11] By the transesterification reaction of a polymer having a structural unit represented by, triaryl trimellitate, a polyfunctional allyl ester and a polyfunctional alcohol with titanium tetraisopropoxide, sodium methylate, zinc acetate, p-toluenesulfonic acid, etc. as catalysts. Expression obtained

[0021]

[Chemical 12]

[0022]

[Chemical 13]

[0023]

[Chemical 14]

[0024]

[Chemical 15]

[0025]

[Chemical 16]

[0026]

[Chemical 17]

[0027]

[Chemical 18] The condensate represented by is exemplified.

It should be noted that a polybasic acid and a pentaerythrite diallyl ether were esterified,

[0029]

[Chemical 19] A polycondensation compound represented by the formula, obtained by polymerizing an acrylate having a carboxyl group or a methacrylate having the same group, and adding allyl alcohol thereto.

[0030]

[Chemical 20] A polymer obtained by polymerizing a polymer having a structural unit represented by, an acrylate having an alcohol group or a methacrylate having the same group, and adding methacrylic acid thereto.

[0031]

[Chemical 21] And the like, and further include divinylbenzyl compounds, trivinylbenzyl compounds, tetrabenzyl compounds and the like.

Further, as a monofunctional compound which is another component of the high hardness resin composition of the present invention, a monofunctional compound having one unsaturated group represented by the formula (2) CH ₂ ═CH—CH ₂ —Y As the functional compound, 2,4-diphenyl-4-methyl-1-pentene,
Examples of monofunctional allyl compounds such as allyl glycidyl ether, glycerin monoallyl ether, ethylene glycol monoallyl ether, allyl benzoate, and allyl acetoacetate are given as general monofunctional compounds (3) CH ₂ = CH-Y Examples of the monofunctional compound having one unsaturated group in which an aryl group is adjacent to the double bond shown are styrene monomer and vinylnaphthalene.

The polyfunctional compound and / or monofunctional compound is mixed with a radical initiator and a filler for polymerizing the compound to obtain a high hardness resin composition. The radical initiator is a known azo compound. , Acetophenone-based or thioxaton-based photoinitiators, organic peroxides, etc., and as the filler, unsaturated polyester alkyd, urethane acrylate, allyl ester, bisphenol type vinyl ester, novolac type vinyl ester and other vinyl esters , A reactive polymer compound such as a macromer obtained by copolymerizing a monofunctional acrylic monomer having a hydroxyl group with another type of acrylic monomer and condensing methacrylic acid to a side chain hydroxyl group, an acrylic monomer, a methacrylic monomer, an allyl monomer, vinyl Low molecular weight compounds such as monomers, Krill beads, polyethylene powder, vinyl chloride powder, urethane acrylate powder, silica, aluminum silicate, aluminum hydroxide, calcium carbonate, talc, mica, etc. may be used, but flame retardants, antioxidants, ultraviolet absorbers, coloring It is optional to add agents and the like.

The high-hardness resin composition containing the polyfunctional compound and / or the monofunctional compound as a main component has a monohydrogen phosphate ester and a monohydrogen phosphate ester in order to prevent warpage and sink marks in the high-hardness resin product produced from this. / Or 2
Hydrogen phosphate ester is added. As the monohydrogen phosphate, di (2-ethylhexyl) phosphate, a compound of formula

[0035]

[Chemical formula 22]

[0036]

[Chemical formula 23]

[0037]

[Chemical formula 24] Examples of the dihydrogen phosphate include mono (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) acid phosphate, 3chloro-2asidphosphoxypropyl methacrylate, and acid phosphonate. Examples include oxypropyl methacrylate and acid phosphooxypolyoxyethylene glycol monomethacrylate. It is said that these phosphoric acid esters have an effect of adhering to a metal, and the inventors of the present invention suppress the curing shrinkage of the high-hardness resin composition by the effect of adhering to a metal, whereby the high-hardness resin product It was found that warpage and sink marks were prevented.

The amount of the monohydrogen phosphate ester and dihydrogen phosphate ester blended is such that the high hardness resin composition 1
If it is less than 0.01 parts by weight with respect to 00 parts by weight, its compounding effect is not seen, and if it exceeds 20 parts by weight, it becomes difficult to separate the molded product of the high hardness resin composition from the mold after curing, so this is It is required to be in the range of 0.01 to 20 parts by weight. In this case, a conventionally known method for reducing shrinkage during curing of a high-hardness resin composition, a dimethylpolysiloxane oil having a molecular weight of about 500 to 10,000 or its carbinol modified product, carboxyl modified product, Method of blending methacryl modified product, epoxy modified product, amino modified product, method of slowly curing it at low temperature, compounded spiro orthoester having unsaturated group directly on spiro ring that expands in volume by radical ring-opening polymerization It is optional to use it in combination with the method.

This high-hardness resin composition can be made into a high-hardness resin molded body by polymerizing and curing it by heating it in a mold, for example, but since it contains hydrogen phosphate ester, it is warped. It can also be free of sink marks. Further, this high hardness resin molded body may be a product obtained by co-crosslinking with the organopolysiloxane composition. This organopolysiloxane composition has an average composition formula of R _m Si, which is usually called silicone oil or silicone raw rubber.
Represented by O _{(4-m) / 2} , R is an alkyl group such as a methyl group, an ethyl group and a propyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group and a tolyl group Selected from a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc. in which some or all of the hydrogen groups bonded to the carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. An unsubstituted or substituted monovalent hydrocarbon group, usually at least 50% of which is a methyl group with 0 to 5
% Vinyl groups and 0 to 50% phenyl groups.

This organopolysiloxane is said to have its terminal blocked with a triorganosilyl group such as a trimethylsilyl group, a dimethylvinylsilyl group, a methyldivinylsilyl group, a methylphenylvinylsilyl group or a hydroxyl group. In order to improve the mechanical properties of the molded product, the polysiloxane composition is usually added with a silica-based filler, a semi-reinforcing agent such as calcium carbonate, talc, mica and aluminum hydroxide. If desired, softeners such as alkoxysilane, terminal silanoldimethylpolysiloxane, and diphenylsilanediol, heat resistance improvers, and colorants may be added to the organopolysiloxane composition.

A radical initiator such as an organic peroxide, an azo compound or a photoinitiator is added to the organopolysiloxane composition in order to cure the composition, which is typically an organic peroxide. And specifically, benzoyl peroxide, dicumyl peroxide,
2,4-dichlorobenzoyl peroxide, monochlorobenzoyl peroxide, di-t-butyl peroxide, 2-butylperbenzoate, 2,5-dimethyl-2,5- (di-t-butylperoxy) hexine,
1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-
Examples thereof include dihydroperoxyhexane, methyl ethyl ketone peroxide, cumyl hydroperoxide, t-butyl hydroperoxide, etc., and any one of these can be selected to give 0.05 per 100 parts by weight of the organopolysiloxane composition. It may be added in the range of up to 10 parts by weight.

In order to obtain a co-crosslinked integrated product of the high hardness resin molded product and the organopolysiloxane composition, for example, the high hardness resin composition is filled in a predetermined dug portion in a mold and heated or After the fluidity is lost by light irradiation or the like, the mold may be filled with an organopolysiloxane composition containing a radical initiator, and heated and pressed. It is possible to easily obtain an integrated molded product that is co-crosslinked with the organopolysiloxane molded product.

However, in order to enhance the bonding between the high-hardness resin molded product and the organopolysiloxane molded product, it is preferable to use a composition that slows down the curing rate of the high-hardness resin composition. As for the composition, the polyfunctional compound may be diallyl terephthalate, triallyl trimellitate or the like having good resonance, or the radical initiator may be a high temperature decomposable type or 1,1-di-t-butylperoxy-3, which is hard to dry. 3,5-trimethylcyclohexane,
t-butylperoxy-2-ethylhexanate, t-
Butylperoxyisobutyrate, t-butylperoxypropyl carbonate, di-t-butylperoxide, etc., and hydroquinone as a chain transfer agent,
P-dimethylaminobenzaldehyde, N-methyldiethanolamine, etc. may be added.

When the high-hardness resin composition and the organopolysiloxane composition are co-crosslinked and integrated, the functional compound concentration of the high-hardness resin component in the high-hardness resin composition may be set to a reference value or more. Well, when this is a polyfunctional compound represented by the general formula (1), the unsaturated group concentration of the polyfunctional compound is 4 × 10 ^-6 mol /
If it is a monofunctional compound represented by the general formula (2) or general formula (3), the unsaturated group concentration of the monofunctional compound is preferably 1.8 × 10 ⁻³ mol / ml or more.

Further, regarding the co-crosslinking integrated molding of the above-mentioned high hardness resin composition and the organopolysiloxane composition according to the present invention, this high hardness resin composition is used as a dug portion for forming a key top portion of a mold. After filling, the mold was filled with the organopolysiloxane composition, heated and pressed to mold the organopolysiloxane composition into a thin-walled movable part and a base part, and these were co-crosslinked and integrated.
The key top portion 2 shown in Fig. 2 is made of a high hardness resin, and the thin movable portion 3, the base portion 4, and the contact portion 5 are formed of an organopolysiloxane composition, and these are completely co-crosslinked and integrated into a push button switch. The advantage that the cover member 1 for a vehicle is easily obtained is provided.

[0046]

EXAMPLES Next, examples and comparative examples of the present invention will be described. Example 1 Formula as polyfunctional compound represented by R ² C = CR-Y as general formula (1)

[0047]

[Chemical 25] , N = 37, molecular weight of 2,700 at both ends of methacryl
0.1% by weight of urethane-modified 1,2-polybutadiene, 1% by weight of diethylene glycol bis (t-butylperoxy) carbonate as a radical initiator, colorant Plastron Toner Black [Product of Dainippon Ink and Chemicals, Inc.] Name] 1% by weight, formula

[0048]

[Chemical formula 26] 35% by weight of thermosetting resin / urethane acrylate oligomer, 32.9% by weight of isobornyl methacrylate,
100 parts by weight of a composition comprising 10% by weight of dimethyloltricyclodecane dimethacrylate and 20% by weight of 2-hydroxy-3-phenoxypropyl acrylate was added to 100 parts by weight of mono (2-acryloyloxyethyl) acid phosphate as a monohydrogen phosphate ester. Kyoeisha Chemical Co., Ltd. product name] was blended in the range of 0.01 to 20 parts by weight to prepare a high hardness resin composition.

Then, this high hardness resin composition was filled in a dug portion for forming a key top portion of a mold heated to 170 ° C. using a dispenser AD3000HV [trade name of Iwashita Engineering Co., Ltd.], Silicone rubber composition KE-951U [trade name of Shin-Etsu Chemical Co., Ltd.] 100 parts by weight of organic peroxide 1,6-bis- (t
-Butylperoxycarboxy) hexane [manufactured by Nippon Akzo Co., Ltd.] 0.8 parts by weight of an organopolysiloxane composition was filled, the mold was closed, and hot pressing was performed at a molding pressure of 200 kg / cm ² for 2 minutes. As shown in FIG. 2, a plate 21 having a high-hardness resin composition 22 on one side and an organopolysiloxane composition 23 on the other side, which are co-crosslinked and integrated.
Was obtained, which was 0.01 to 20 per 1 hydrogen phosphate.
Since it was added in the range of parts by weight, there was no deformation such as warpage or sink marks, the joint surface was extremely strong, and neither was separated.

Comparative Example 1 Same as Example 1 except that the addition amount of mono (2-acryloyloxyethyl) acid phosphate as monohydrogen phosphate in the high hardness resin composition in Example 1 was less than 0.01 parts by weight. As a result, a plate 41 having a high-hardness resin 42 on one side and an organopolysiloxane composition 43 on the other side was obtained.These bonding surfaces were extremely strong, and the two did not peel off. As shown in FIG. 4, the high hardness resin surface 42 was warped or sinked.

Comparative Example 2 Same as Example 1 except that the addition amount of mono (2-acryloyloxyethyl) acid phosphate as monohydrogen phosphate in the high hardness resin composition in Example 1 was 20 parts by weight or more. When this molded product was treated with the above method and tried to be peeled off from the surface of the mold to which nickel was transferred, it completely adhered to the mold and could not be released normally.

Example 2 Formula represented by the general formula (1) R ² C = CR-Y

[0053]

[Chemical 27] A polyfunctional compound represented by (n = 2 to 3, molecular weight 913) 20
% By weight and 1,6-bis- (t- as radical initiator
Butyl peroxycarboxy) hexane 1% by weight, styrene cross-linked powder SPG-70C [trade name of Soken Chemical Industry Co., Ltd.] 19% by weight, 1,4-butanediol 180 g, orthophthalic acid 220 g and fumaric acid 100 g are condensed. Obtained acid value
30 parts by weight of 55 unsaturated polyester alkyd, 15% by weight of 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, and 15% by weight of isobornyl acrylate were added to 100 parts by weight of acid phosphooxy as dihydrogen phosphate ester. A high hardness resin composition was prepared by mixing 0.1 to 20 parts by weight of polyoxyethylene glycol monomethacrylate.

Then, this was filled in the dug portion for forming the key top portion of the mold heated to 160 ° C. using a dispenser, and when the fluidity was lost, the mold was closed,
A low-viscosity silicone rubber / X is applied to the dug part of the mold for forming the thin wall part of the mold and the base part through the runner part.
-93-532 [Shin-Etsu Chemical Co., Ltd. trade name] 100 parts by weight of an organopolysiloxane composition containing 0.8 parts by weight of t-butylperoxyisobutyrate is filled by injection molding to obtain a resin pressure of 25 kg / When molded under the condition of cm ² , there is no warp or sink deformation in the key top part made of high hardness resin, the elastic material does not wrap around the key top part, the joint is extremely strong and both A cover member for a push button switch which was not peeled off was obtained.

Example 3 50% by weight of a monofunctional compound of the general formula (2) CH ₂ ═CH—CH ₂ —Y, allyl benzoate (manufactured by Daicel Chemical Industries, Ltd.), and lauroyl as a radical initiator. 1% by weight of peroxide [manufactured by Kayaku Akzo Co., Ltd.] and 1% by weight of colorant, plastron, toner, yellow, O-6661 [trade name of Dainippon Ink and Chemicals, Inc.] and in Example 2 To 100 parts by weight of the composition containing 48% by weight of the unsaturated polyester alkyd used, the formula

[0056]

[Chemical 28] A high hardness resin composition was prepared by adding 0.5 weight part of a monohydrogen phosphate ester represented by.

Then, this composition was filled in the concave portion of the mold heated to 110 ° C. using a dispenser, and when the fluidity was lost, the silicone rubber composition KE-9 was used.
51U (supra) 100 parts by weight of p-chlorobenzoyl peroxide [manufactured by NOF CORPORATION] was added to this mold and the organopolysiloxane composition was filled into the mold, and the mold was closed to 200 kg / cm. ^After pressurizing and heating at a molding pressure of ² for 5 minutes, a container 31 in which the concave portion 32 shown in FIG. 3 is made of high hardness resin and the bottom surface 33 is made of organopolysiloxane is obtained, but there is no warp or sink mark in this concave portion. The joint surface was extremely strong and did not separate from each other.

Comparative Example 3 The high hardness resin composition of Example 3 containing 20 parts by weight or more of this monohydrogen phosphate ester and the polysiloxane composition were integrally molded under the same processing conditions as in Example 3. However, in this case, the molded body was stuck to the mold and could not be released.

Example 4 50% by weight of styrene as a monofunctional compound represented by the general formula (3) CH ₂ ═CH—Y, 1% by weight of a radical initiator, lauroyl peroxide and a coloring agent, plastron, toner,
Red 04715 [Product name of Dainippon Ink and Chemicals, Inc.] 1% by weight and formula

[0060]

[Chemical 29] 100 parts by weight of a composition obtained by adding 48% by weight of urethane acrylate shown in

[0061]

[Chemical 30] Was added to 0.5 part by weight of monohydrogen phosphate ester to prepare a high hardness resin composition.

Then, this composition was filled in the concave portion of the mold heated to 120 ° C. using a dispenser, and when the fluidity was lost, the mold was filled with the silicone rubber composition KE-951U (previously Output) 100 parts by weight of organic peroxide / p
When an organopolysiloxane composition containing 0.4 parts by weight of -chlorobenzoyl peroxide and 0.4 parts by weight of t-butyloxypivalate was filled and heated under a molding pressure of 200 kg / cm ² for 2 minutes, one side had high hardness. Since the opposite surface of the resin was an organopolysiloxane elastic body and both were extremely strongly adhered, they could not be separated from each other, and a plate having no deformation such as warpage or sink mark was obtained on the high hardness resin molded body.

Comparative Example 4 In the high hardness resin composition of Example 4, the amount of the monohydrogen phosphate ester was 20 parts by weight or more, and the molded body could not be released from the mold after molding. Comparative Example 5 When the amount of the monohydrogen phosphate ester added to the high hardness resin composition of Example 4 was less than 0.01 parts by weight, warpage and sink marks were generated on the surface of the high hardness resin.

Example 5 Triallyl trimellitate [manufactured by Daicel Chemical Industries, Ltd.] 10% by weight as a polyfunctional compound represented by the general formula (1) and aceto as a monofunctional compound represented by the general formula (2). Allyl acetate [manufactured by Daicel Chemical Industries, Ltd.] 40% by weight,
And radical initiator Lauroyl peroxide 0.4
Wt% and formula

[0065]

[Chemical 31] In 100 parts by weight of a composition consisting of 49.6% by weight of urethane acrylate,

[0066]

[Chemical 32] 0.5 parts by weight of monohydrogen phosphate ester and 0.5 parts by weight of mono (2-acryloyloxyethyl acid) phosphate [trade name of Kyoeisha Chemical Co., Ltd.] as dihydrogen phosphate ester are mixed to obtain a high hardness resin composition. Prepared.

Then, this composition was filled in the dug portion for forming the key top portion heated to 120 ° C. using a dispenser, and when the fluidity was lost, the mold was closed,
The silicone rubber composition X-93-53 is applied to the dug portion for forming the thin portion and the base portion of the mold through the runner.
2 (above) 0.4 part by weight of p-chlorobenzoyl peroxide and 100 parts by weight of t-butylperoxypivalate
An organopolysiloxane composition containing 0.4 parts by weight was filled by an injection molding method and molded under the conditions of a resin pressure of 30 kg / cm ² and a molding time of 2 minutes. Thus, a cover member for a push button switch was obtained in which there was no deformation, the elastic material did not wrap around the key top portion, the bonding portion was extremely strongly adhered, and the two did not separate.

[0068]

INDUSTRIAL APPLICABILITY The present invention relates to a high-hardness composition and an integrally molded product of the high-hardness composition and an organopolysiloxane composition. As described above, the high-hardness resin composition is represented by the general formula (1). A functional compound and / or a monofunctional compound represented by the general formula (2) or (3), to which a radical initiator, a filler, and a monohydrogen phosphate ester and / or a dihydrogen phosphate ester are added. An integrally molded product of the organopolysiloxane composition and the organopolysiloxane composition is heated to co-crosslink with the high-hardness resin composition and the organopolysiloxane composition containing a radical initiator to form an integrally molded product. This high hardness resin composition is characterized by the fact that 1 hydrogen phosphate, 2
Since hydrogen phosphate is added, this molded body has an advantage that it is not deformed due to warpage or sink marks, and it is co-crosslinked with an organopolysiloxane composition integrally molded with this molded body. Therefore, there is an advantage that the joint between the two is extremely strong and they are not separated.

[Brief description of drawings]

FIG. 1 is a vertical sectional view of a cover member for a push button switch according to the present invention.

FIG. 2 shows a vertical sectional view of a plate made in Example 1 of the present invention.

FIG. 3 shows a vertical cross-sectional view of a container made in Example 3 of the present invention.

FIG. 4 shows a longitudinal sectional view of a plate made in Comparative Example 1.

[Explanation of Codes] 1 ... Push button switch cover member, 2 ... Key top part, 3 ... Thin movable part, 4 ... Base part, 5 ... Contact part, 21 , 41 ... Plate, 22, 42 ... High hardness resin composition , 23 ... Organopolysiloxane composition, 31 ... Container,
32 ... recess, 33 ... bottom.

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[Procedure amendment]

[Submission date] December 22, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

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Therefore, the inventors of the present invention have previously proposed a cover member for a push button switch in which a high hardness resin composition for a key top is integrally formed with a thin movable portion, a base portion, a contact portion and the like made of a rubber-like elastic body. (Japanese Patent Laid- Open No. 3-155391)
(See Japanese Patent Publication). Explaining this in detail, a high-hardness resin composition comprising a compound having a plurality of functional groups capable of radical resonance represented by a methacryloyl group, an allyl group and a mesalyl group and an organic peroxide (here, a high-hardness resin composition Is a liquid material or a paste in which IRHD is 90 ° or more upon curing.) Is filled in the dug portion for forming the key top portion of the die, and the synthetic rubber containing the organic peroxide is placed in the die. This is a cover member for a push button switch which is filled in the thin movable part and the dug part for forming the base part, and pressed and heated to be integrally molded in the mold by co-crosslinking. The key top portion is excellent in softness, and the thin-walled movable portion that is agile in the soft pressing feeling and the responsiveness of the deformation restoration accompanying the pressing release are integrated. In addition, JP-A-5-6
The method of manufacturing a cover member for a push button switch disclosed in Japanese Patent No. 7410 proposes the timing of integral molding of a high hardness resin composition and synthetic rubber proposed in Japanese Patent Laid-Open No. 4-355004, which will be described in detail. The high hardness resin containing the organic peroxide is filled in the dug portion for forming the key top portion of the heated die,
At this time, after the high-hardness resin has lost its fluidity, synthetic rubber containing organic oxide is filled in the dug portion forming the thin-walled movable part and base part, and co-crosslinking is integrally molded in the mold. By doing so, the responsiveness of the deformation restoration becomes more agile, and the fatigue resistance against deformation increases. Regarding this, further, in JP-A-5-92805, a high-hardness resin composition, particularly a key top portion made of a high-hardness silicone resin having a diphenyl skeleton or a methylphenyl skeleton, a thin-walled movable portion made of silicone rubber, a base portion, a contact point, A cover member for a push button switch, which is integrally formed by co-crosslinking with the section, is proposed.

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Claims (4)

[Claims] 1. A compound represented by the general formula R ² C = CR-Y (wherein R is a hydrogen atom or a monovalent hydrocarbon group, and Y is a compound main chain consisting of an organic atom chain and / or a siloxane chain) A polyfunctional compound having at least one hydrogen atom on a carbon atom adjacent to a bond or having two or more unsaturated groups adjacent to an aryl group on a double bond, a radical initiator, a filler and a monohydrogen phosphate A high hardness resin composition comprising 0.01 to 20 parts by weight of an ester and / or a dihydrogen phosphate ester. 2. The general formula CH ₂ ═CH—CH ₂ —Y (where Y is a compound main chain composed of an organic atom chain and / or a siloxane chain).
And a monofunctional compound having one unsaturated group and /
Alternatively, a monofunctional compound having one unsaturated group in which an aryl group is adjacent to a double bond represented by the general formula CH ₂ ═CH—Y (Y is the same as above) is added to a radical initiator, a filler and a monohydrogen phosphorus compound. Acid ester and / or dihydrogen phosphate ester
A high hardness resin composition comprising 0.01 to 20 parts by weight. 3. A high-hardness resin composition according to claim 1 and / or a high-hardness resin composition according to claim 2 and an organopolysiloxane composition containing a radical initiator are formed by co-crosslinking and integral molding. And molded body. 4. A key top part made of the high hardness resin composition of claim 1 and / or the high hardness resin composition of claim 2, and a thin movable part made of an organopolysiloxane composition containing a radical initiator. A cover member for a push button switch, which is integrally formed with a base portion by co-crosslinking.