CN1090653C - Thermoset resin composition and composite body of same and polysiloxane rubber - Google Patents

Abstract

The present invention discloses a novel thermosetting resin composition which is suitable for preparing two parts of complexes of an integral mould, which comprises a first part for solidifying silicon rubber and a second part for solidifying thermosetting resin, and an adhesive layer is inserted into the interface position. The thermosetting resin composition comprises the following components by weight: 100 portions of unsaturated polyester resin, 20 to 50 portions of alkylened unsaturated polymerisable compound, such as diallyl phthalate, 5 to 30 shares of epoxy resin, 2 to 20 portions of melamine resin, 0.1 to 2 portions of free radical reaction solidifying agent which is an organic peroxide and 0.1 to 2 portions of acidic catalyst, such as an aromatic sulphonic acid derivative.

Description

Compositions of thermosetting resin and with two part complex bodys of silicon rubber

The present invention relates to a kind of compositions of thermosetting resin, also relate to a kind of two part complex bodys, this complex body comprises the first part of solidified silicon rubber and the second section of compositions of thermosetting resin, and this two part integrally combines and do not insert binder layer.More particularly, the present invention relates to can with a kind of compositions of thermosetting resin of silicon rubber surface bonded, this resin combination is cured thereon, even and also can present high bonding strength when not using any tackiness agent.

Two part complex bodys are the trend of development in recent years, this complex body comprises by having Shore A hardness in the first part with caoutchouc elasticity that the rubber of 30 to 80 scopes is made, and have Shore D level hardness and be at least 40 solidified and the hard made second section of resin, as possible, do not use tackiness agent, and making second section integrally be attached to first part, this two part complex bodys are necessary in many application sometimes.One of representative instance of such two portions complex body is the so-called button coating member that is used for the push-button control dish of various electronic machines.Usually the press button coating member has continuous structure, it comprises many unit button switches, wherein each all has the structure with the vertical cross-section diagram explanation of Fig. 7, each press button comprises basic unit's parts 75, one lifting piece 74 and a button top basic unit 72 by the elastomeric material integral die, and the button top layer 71 of making and be attached to button top basic unit 72 by hard resin material, by the movably point of contact 76 that electric guide rubber material is made, it is attached to the lower surface of button top basic unit 72.When button top layer 71 persons' of being operated finger tip down on time, lifting piece 74 is just crooked, and movably point of contact 76 just contacts with a pair of fixed contact point (not shown) on the following circuit card (not shown), the topped parts of press button are installed on basic unit's part 75 in the circuit board, so that connect the circuit between the fixed contact point.When removing of button top layer 71 by power, then owing to be subjected to the elastic force of elastomeric material, make lifting piece 74 return to not by state, make this movably point of contact 76 upwards be pulled away from fixed contact point and breaking circuits.

Form this basic unit's parts 75, the elastomeric material of lifting piece 74 and button top basic unit 72 requires to have Shore A hardness to be 80 or to be lower than 80, presses the good working performance in the operation and guarantees good position-adjustable in the topped parts of circuit card are installed above-mentioned so that guarantee.In various types of elastomeric materials, in most of the cases, with regard to their good electrical property, accurate moldability and the weather resistance of moving in repeated flex and disengagement, silicon rubber is preferred.

On the other hand, use by to have preferred Shore D level hardness be 40 or make button top layer 71 greater than 40 hard thermosetting resin.This is because when button top layer 71 is by elastomeric material and other parts when integrally molded, the top surface of this button top layer 71 more or less has elastomeric material inherent viscosity, down to the slipperiness of having disturbed the button pressing operation.In addition, the fatty movement of discharging from operator's finger tip absorbs and infiltrates and cause decolouring of button top layer and the performance that rubber makes by the elastomeric material of the top surface of this button top layer 71 and reduces for example physical strength.When because the migration by button top layer 71 and button top basic unit 72 when making movably point of contact 76 below the button top layer by fatty manure contamination, then cause to form the movably resistance increase of the electric conductivity elastomeric material of point of contact 76, this has just reduced the usability of this switch.

Certainly the piece material that is used for button top layer 71 is by separately preparation of thermosetting resin, and this piece material is adhered on the upper surface of rubber button top basic unit 72 by using binding agent.Yet this method is unpractiaca, because if do not mention because of the caused shortcoming of unfairness when boning between rubber button top basic unit 72 and the hard resin button top layer 71, has also increased the complicacy of the topped parts manufacturing processed of this press button.Above-mentioned situation has constituted that to tend to the topped parts of press button recently be to make two part complex bodys rather than use tackiness agent that the button top layer 71 of resin is bonded to reason in the basic unit 72 of rubber button top with Unitarily molded.

In prior art, done various trials and suggestion so far, thermosetting resin is not used tackiness agent, use the method for the chemical reaction that forms chemical bond that thermosetting resin integrally is attached on the silicon rubber part surface.Such compositions of thermosetting resin be included among the open 6-309988 of Japanese Patent disclosed those, it is the high rigidity silicone resin.Comprise the methyl silicone resin, phenyl silicones resin, dimethyl diphenyl silicone resin or the like.The compositions of thermosetting resin of other types be included among the open 6-60767 of Japanese Patent disclosed those, comprise multi-functional compounds, the concentration of its unsaturated group is at least 6 * 10 ^-4Mole/milliliter, it mixes with organo-peroxide to have the thermofixation performance.The example of above-mentioned multi-functional compounds has Ethylene glycol dimethacrylate, Diethylene Glycol dimethacrylate etc.

Above-mentioned can with the prior art of the thermosetting resin of silicon rubber chemical bonding in each all has the merits and demerits of oneself.For example, the silicone resin of disclosed high rigidity is compared with poly-(methyl methacrylate) resin and polycarboxylate resin in the open 6-309988 of Japanese Patent, and each all has the very high transparency, and the part that resin is made have total light transmittance be 90% or even higher so that can prepare the colored part of any distinct color.In addition, the linear shrinkage that these resins present when molded is equivalent to silicon rubber haply, with distortion or the distortion that causes Unitarily molded two portions complex body to cause less than the difference because of the molded contraction between two portions.On the other hand, the physical strength of these silicon rubber, especially its shock strength is lower, when the thickness of this button top layer 71 hour, during less than 2.3mm, then when a mechanical shock test, the crack appears sometimes on button top layer 71 for example in the topped parts of a press button, these topped parts are fallen from about 2 meters eminences and are used on the topped floor of resin sheet when this test, therefore must carefully carry out when handling the topped parts of this press button.

In contrast, have quite high physical strength usually at the open disclosed thermosetting resin of 6-60767 of Japanese Patent, so that do not have and pass through above-mentioned mechanical shock test difficultly as the resin inherent nature.Yet the Application Areas of these resins is restricted, because the Shore D level hardness of this resin is 50 to 60, so even this resin surface is easy to the indentation that forms because of the scratch that is subjected to fingernail or tip of a pencil.In addition, these resins also have the other problem that relates to molded contraction, and it often has big linear shrinkage to 7-8%, as illustrated to 8E with reference to figure 8A, this figure with cross-sectional illustration prepare the topped parts of press button with the Unitarily molded program of silicon rubber.That is, shown in Fig. 8 A, flowable resin combination 82 is injected into the pouring hole of counterdie 83 from distributer nozzle 81, to fill pouring hole (8B with the aid of pictures).As shown in Fig. 8 C, just the heating pouring hole of counterdie 83 and thermally curable resin composition with after forming solidified button top layer 86, the pouring hole that uncured silicone rubber material plate 84 is set up to cover counterdie 83 also closes up this metal mold with patrix 85 (8D with the aid of pictures), be compression molded into solidified silicon rubber part, this part comprises basic unit's parts 75, lifting piece 74 and button top basic unit 72, shown in Fig. 8 E, this part is the button top layer 86 that integrally is attached to resin manufacture.

Shown in Fig. 8 C, because the big mould shrinkage of resin combination 82, inevitably formed big clearance space 90 with the wall of the pouring hole of counterdie 83 in cured resin part around along 86, make shown in Fig. 8 D, silicone rubber material 84 pushes very naturally and enters and fill this clearance space 90 round cured resin button top layer 86 under pressing mold, and solidify therein and be bonded to resin part 86, shown in Fig. 8 E, joint face between two portions can not be evenly, so that between two parts shown on the sidewall at button top 86 irregular connecting thread is arranged.Yet, when molded,, finally can cause the crooked or distortion of two portions complex body owing between rubber part 72 and resin part 86, have big difference aspect the molded contraction.

In addition, disclosed thermosetting resin among the open 6-60767 of Japanese Patent, when with the open 6-309988 of Japanese Patent disclosed those relatively the time, in the fast setting process, lost the binding ability with silicon rubber, make with the Unitarily molded process of silicon rubber part changeable inadequately.And resin combination does not have high degree of transparency so that makes with the molded button top layer of resin combination distinct color to be arranged.

Therefore, an object of the present invention is to provide a kind of novelty and improved compositions of thermosetting resin, said composition can be integrally molded with silicon rubber, and do not use any binding agent, to obtain a kind of two portions complex body, this complex body does not have because of there is the shortcoming that big-difference produced of molded contraction between resin combination and rubber composition, wherein cured resin partly has good physical strength and has high-clarity, therefore can make the resin portion branch painted by any desired color.Another object of the present invention provides a kind of two portions complex body, it comprises by prepared cured resin part of top mentioned novel resins composition and cure silicone rubber part, this two part integrally and directly combines, and does not insert adhesive layer therein.

Therefore, be suitable for integral body and be attached to the cure silicone rubber part, and be a kind of uniform mixture at the compositions of thermosetting resin of the present invention that does not insert an adhesive layer at the interface, this mixture comprises:

(a) unsaturated polyester resin of 100 parts of weight;

(b) the undersaturated polymerisable compound of the alkylene of 20 to 50 parts of weight;

(c) Resins, epoxy of 5 to 30 parts of weight;

(d) melamine resin of 2 to 20 parts of weight;

(e) solidifying agent of the free radical reaction of 0.1 to 2 part of weight; With

(f) an acidic catalyst of 0.1 to 2 part of weight.

By two portions complex body provided by the present invention, for example the topped parts of a press button are an integral body, and it comprises:

(A) by one first molded cured portion of rubber composition, wherein the organopolysiloxane molecule has a vinyl groups that is attached to the Siliciumatom of molecule at least; With

(B) by the second molded cured portion of compositions of thermosetting resin, it is a kind of uniform mixture, and this mixture comprises:

(a) unsaturated polyester resin of 100 parts of weight;

(b) the undersaturated polymerisable compound of the alkylene of 20 to 50 parts of weight;

(c) Resins, epoxy of 5 to 30 parts of weight;

(d) melamine resin of 2 to 20 parts of weight;

(e) solidifying agent of the free radical reaction of 0.1 to 2 part of weight; With

(f) an acidic catalyst of 0.1 to 2 part of weight,

First part and second section be link together and do not insert adhesive layer at the interface at this.

Each all represents with vertical cross section Figure 1A in 1E, each step in the topped parts process of the Unitarily molded press button of the compositions of thermosetting resin of the application of the invention.

Fig. 2 A is the vertical cross section brief description, fall hammer and the test method of the shock strength of specimen by the conical head that lands, and Fig. 2 B is the axial section that hammer falls in this conical head.

Each explanation of Fig. 3 A and 3B has smooth interface or has the bonding state at irregular waviness interface between thermosetting resin and silastic-layer vertical cross section.

Fig. 4 is the vertical cross section that is used for the light guide member of dark a kind of press button of locating.

Fig. 5 is the axial section of the resin cover plate of whole preparation elasticity assembling.

Fig. 6 is the axial section of the pallet of two portions complex body of being made up of trying to get to the heart of a matter of resin pallet and rubber system of expression, and the cup of beverage is housed on it.

Fig. 7 is the vertical cross section of the structure of the topped parts of expression press button.

Fig. 8 A illustrates with vertical cross section to each of 8E and represents, uses each step of the Unitarily molded topped parts process of press button of traditional compositions of thermosetting resin.

Be attached to the cure silicone rubber surface and do not insert sticking therebetween such as the top integral body that is suitable for of summarizing The thermosetting resin composition of mixture layer is a kind of uniform mixture, and this mixture contains and comprises component (a) To the basis of (f), above-mentioned each component has the weight ratio of regulation with respect to component (a).

Component (a) is a kind of unsaturated polyester resin, and it is not limited to particular type, but can be the isophthalic diformazan The mylar of acidic group, the mylar of phthalic acid base, the mylar of bis-phenol base or other do not have The special type that limits. The product that belongs to such different commercialization can buy on market, and Can with product comprise following trade name Estars 1510C, CL1270 and CO600-1 (each product Product are all produced by Mitsui-Toatsu Kagaku company), Upicas 2035,2239 and 2253 (each Plant all and produced by Nippon Upica company), Polymal (is produced by Takeda Pharmaceutical company ), Palylite (being produced by Dai-nippon Ink chemical company), Rigolac is (by Showa High-Polymer company produces) etc. From these commercial products, select unsaturated polyester resin certainly to rely on In the specific requirement by resin manufacturing performance partly, for example thoroughly high according to two part complex instructions for uses Bright property, good resistance to fracture.

Component (b) be a kind of undersaturated polymerisable compound of alkene or normally a kind of vinyl or The pi-allyl compound, it has dual function, and one side is as the crosslinking agent of this unsaturated polyester resin, in addition One side is as the promoter of combination between resin surface and this silastic surface. This kind alkeneization is undersaturated can The example of the compound of polymerization comprises styrene, i.e. vinyl benzene, vinyl methyl, phthalic acid diene Propyl diester, cyanuric acid triallyl ester etc., wherein, phthalic acid diallyl with regard to its low evaporation property Ester is preferred, and has improved anti-friction wiping by the prepared cured portion of resin combination of the present invention The property, it is suitable for molded accurately molded article for example has the press button coating member as representative products, and Then styrene is with regard to its curing of descending the resin combination compound with it about the lower temperature room temperature Preferably, to satisfy the requirement of preparation filler or packing ring. Heat resistance with regard to curable resin composition changes And then speech, then the cyanuric acid triallyl ester is preferred, with thermosetting resin composition of the present invention and cyanogen urine The acid triallyl ester is compound, for example is to be suitable for making pallet to have the heat that anti-skidding silicon rubber is tried to get to the heart of a matter with loading The beverage cup, as shown in Figure 6. Except above-mentioned various monomeric compounds as the component (b), when solid After the change, but partly require certain flexibility with the resin manufacturing part demoulding resin manufacturing of improved while of performance The time, sometimes use for example PVOH dimethylacrylate of long chain diol compound and (methyl) acrylic acid Formed diester is favourable, and its use amount is that the composition (a) of per 100 parts of weight uses 10-20 part Weight.

The component of thermosetting resin composition of the present invention (c) is epoxy resin, and this resin is for improvement of the resin group The mechanical strength of the cured portion of compound also is used for reducing the molded shrinkage of resin combination. Various suitable Commercial product all available on market, comprising: with commodity Epiol NPG-100 (Nippon by name The product of grease company) the neopentyl glycol diglycidyl ether of selling is with commodity Epiol P-by name The propane diols diglycidyl ether that 400 (products of above-mentioned company) are sold so is Epolite by commodity 3002 (products of Kyoei chemical company) are sold, and are added with a kind of two rings of 2 moles of bisphenol-A peroxide Oxygen glycerin ether or so-called BP-A diglycidyl ether are with commodity Epolite 40E (above-mentioned company by name Product) the ethylene glycol bisthioglycolate Synthesis of Oligo Ethylene Glycol of selling etc. Although any in these epoxy resin is all available In the prescription of thermosetting resin composition of the present invention, but just in molding process resin combination crosslinked The promotion of reaction and prevent resin combination be heated flavescence and opinion is preferably used in molecular structure and epoxy Group also has the epoxy resin of a vinyl group together. A kind of epoxy resin that contains vinyl like this The example of commercial product comprise the commodity Blenmar that exists with the glycidyl methacrylate form G (product of Nippon grease company), the commodity that exist with diethyllaminoethyl methacrylic acid ester-formin Lite Ester DE (product of Kyoei chemical company) exists with the glycidyl methacrylate form Commodity Lite Ester G (product of above-mentioned company) and other commodity.

Component (d) is melamine resin, although with regard to during the curing reaction, because gas produces caused little trouble And the butylated melamine resin of opinion hydroxyl is preferred, but can also be from methylolated melamine resin, hydroxyl In the butylated melamine resin of butylated melamine resin and methylol-hydroxyl without particular limitation freely Select. Some example of the suitable commercial product of melamine resin comprises Cymels 303,701 and 232 Hes Micoat 506 (every kind all is the product of Mitsui Cyanamide company), (every kind all is 21R and 120 The product of Mitsui Toatsu Kagaku company) and the product of other code names.

Component (e) is the curing agent of a kind of free radical reaction, perhaps also is exactly, and a kind ofly reacts for free radical Initator. Organically peroxide compound is generally used for this purpose, and this class compound comprises the mistake of ketone Oxide, peroxy ketal, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxide Change ester etc., consider the requirement of solidification temperature and hardening time, therefrom select. Just with its chemical combination The good storage property of resin combination and its relatively shorter molded circulation and opinion peroxy ketal and mistake Oxide ester is preferred. Hydrogen peroxide and dialkyl peroxide normally are unwell to high circulation production Purpose, because it has one minute higher half period temperature, so-called half period temperature is in this temperature Lower, the half period of the thermal decomposition of peroxide compound is 1 minute.

Some example that is suitable as the peroxide compound of component (e) comprises: the methyl ethyl ketone peroxidating Thing (Permek N), two (spy-butyl peroxy-3,3, the 5-trimethyl) cyclohexane (Perhexa of 1,1-3M), just-butyl-4, two (spy-butyl peroxy) valeric acid esters (Perhexa V) of 4-, 2,2-pair (special-Butyl peroxy) butylene (Perhexa 22), benzoyl group peroxide (Niper BW), m-three oily basic peroxidating Thing (Niper BMT-K40), spy-butyl peroxy isopropyl carbonic ester (Perbutyl I) etc., wherein Each is the product of Nipon grease company.

At last, component (f) is a kind of acidic catalyst, and it is as a kind of curing of the melamine resin of component (d) Accelerator. Acidic catalyst can be aromatic sulphonic acid type or phosphatic type. The example of suitable commercial product The Catalyst 4050 that comprises the aromatic sulphonic acid type, and the Catalyit 296-9 of phosphatic type, each It all is the product of Mitsui Cyanamide company.

Thermosetting resin composition of the present invention certainly can be at random by with a kind of suitable organic or do not have Machine colouring agent or pigment combination and painted, the example of organic pigment, such as the phthalocyanine orchid, dual-azo yellow etc. do not have The example of machine pigment, such as titanium dioxide, carbon black, Prussia orchid, ultramarine, cobalt orchid etc. These colouring agents Also can be combined in the rubber composition, be made and thermosetting resin of the present invention by this rubber composition Composition obtains the cure silicone rubber part of the present invention's two part complexs together.

Be to form thermosetting resin composition of the present invention, the amount of each in the above-mentioned basis with respect to Component (a) must be at the weight ratio range of defined. For example, unsaturated as the alkeneization of component (b) The amount of polymerisable compound, by per 100 parts of weight components (a), the group of 20 to 50 parts of weight is arranged Divide (b). When the amount of component (b) with respect to the amount of component (a) very little the time, the thermosetting resin composition can not be complete Curing or its solidify widely delay and can not be attached to well on the silicon rubber part. On the other hand, when Component (b) is measured when excessive, after then solidifying, can cause that the mechanical strength of thermosetting resin reduces.

As the amount of this epoxy resin of component (c), by the component (a) of per 100 parts of weight, 5 to 30 In the scope of part weight. When the amount of component (c) too hour, then the thermosetting resin composition will when molded Big shrinkage is arranged, after curing, reduce resin combination and mechanical strength simultaneously. Work as on the other hand component When amount (c) was too big, then the thermosetting resin composition did not have molded contraction, so that take out from this metal pattern This is molded has any problem during with the resin part of solidifying, and causes productivity ratio and the tree of molding process of the present invention The molded product percent of pass of fat composition or two parts complex descends.

As the amount of the melamine resin of component (d), by the component (a) of per 100 parts of weight, be 2 to 20 In the scope of part weight. When the amount of component (d) very little the time, the cured portion of resin combination is to the silicon rubber table The bond strength of face is not high enough, and when the amount of component (d) is too many, owing at molded and setting up period gas is arranged Body is overflowed and is made the firming body of thermosetting resin composition sometimes have bubble.

Amount as the curing agent of the free radical of component (e) reaction is relevant with this curing agent type, presses per 100 The component (a) of part weight is in the scope of 0.1 to 2 part of weight. When the amount of group part (e) very little the time, thermosetting The property resin combination can not fully solidify, and when the amount of component (e) was too many, resin combination had greatly Molded contraction, and cause the molded of resin combination and solidify forming crack or inferior profile in the part.

As the amount of the acidic catalyst of component (f), by the component (a) of per 100 parts of weight, be 0.1 to arrive In the scope of 2 parts of weight. When the amount of component (f) very little the time, this melamine resin can not solidify fully, like this Just reduce the bond strength between cured resin part and the silicon rubber part. On the other hand, when component (f) Measure when too many, the curing of melamine resin is accelerated excessive, so that the firming body of thermosetting resin composition sometimes Because gas forms bubble is arranged.

Two parts complex of the present invention is a firmly integral body, and it comprises above-mentioned thermosetting resin combination The cured portion of thing and cure silicone rubber part, it is not have insertion to appoint by form chemical keyboard therebetween What bonding layer. Can suppose that above-mentioned chemical bond is by being bonded to the vinyl base of the silicon atom in the silicon rubber Reaction between group and the compound of the alkene unsaturated polymerizable in the thermosetting resin composition and forming . Much less, the surface of resin part and this silicon rubber part needn't be always smooth, can be crooked Or rough, as long as between two parts, can obtain once solid contact-making surface passable.

Although there is no particular limitation, the Shore D level of the firming body of thermosetting resin composition of the present invention Hardness should be 60 or be higher than 60.

The silicon rubber of two parts complex of the present invention partly obtains by rubber composition is molded, Each of organic polysilane molecule in the said composition has a vinyl that is bonded to silicon atom at least Group is as in methyl vinyl silicone rubber, diphenyl divinyl silicon rubber etc. Rubber composition (common by the silicone rubber compound of 100 parts of weight and the free radical reaction curing agent of 0.5 to 5 part of weight A kind of organic peroxide) combination and the preparation. When the amount of curing agent very little the time, certain silicon rubber group Compound can not solidify fully, and when the amount of curing agent was too many, the curing reaction of rubber composition carried out Cause too soon the trouble of sintering.

As required, rubber composition can be randomly with limit the quantity of 0.5 to 3% weight for example Colouring agent mixes. In addition, rubber composition can with light scattering agent, ageing inhibitors etc. are to limit the quantity of Situation is mixed.

The cure silicone rubber part that forms two portions complex body of the present invention should have Shore A hardness in 30 to 80 scopes, and this is decided by the service condition that complex body is concrete.For example, when two portions complex body is the press button coating member, consider various factors, for example form of the size of lifting piece and this button top basic unit and the arrangement of size and unit button switch, the Shore A hardness of this silicon rubber part is preferably in 30 to 60 scope.When two portions complex body of the present invention is to be used for when putting the pan arrest of beverage cup, vase frame etc., when it has the general flat shape of silicon rubber part, according to the desktop on the silicone rubber based surface of contact or the condition on ground, and the base he require for example intensity compensation, the requirement of stability of strutting system or the like, the Xiao A hardness of silicon rubber part can be chosen as in 30 to 80 the scope.

Other application of two portions complex body of the present invention comprise, the resinous toy that for example has rubber part, the resinous hammer that has a Rubber end has the silicone rubber based coupling device of a resinous framework and thermo-sensitivity roller and the various resinous goods that wave on the table that are placed on that are installed in as preventing in the shipping ship that it from sliding on the table.These two parts complex bodys can carry out secondary processing, and for example as required by using printing-ink or coating composition to print, the vehicle resin in the said composition is the resin of polyester based or polyurethane-base preferably.

Below, get the topped parts of press button and be described in more detail two portions complex body of the present invention as typical example.

Much less, for the topped parts of press button, relate to the shape and size of button top layer, the row of pressing and other factors of unit switch have multiple design.For example, this button top layer can be designed to have thickness be 0.5 to 50mm and the area of plane be 0.3 to 5000mm ²Square, square, circle or oval in shape.This lifting piece can be designed to not only be used to connect basic unit's part and this button top basic unit, and can be to have the protrusion shape that is used for crooked and the elastic class dome of restorative shape.

This button top layer is to form by compositions of thermosetting resin of the present invention is molded, said composition comprises the unsaturated polyester resin of per 100 parts of weight, the undersaturated polymerisable compound of alkylene that 20 to 50 parts of weight are arranged, the Resins, epoxy of 5 to 30 parts of weight, the melamine resin of 2 to 20 parts of weight, an acidic catalyst of the solidifying agent of the free radical reaction of 0.1 to 2 part of weight and 0.1 to 2 part of weight.When the main body of the topped parts of press button that comprise basic unit part, lifting parts and button top layer be by rubber composition be molded as such size so that its when having the mechanical property that is enough to actual use and intensity, then the thickness of button top layer preferably is 0.5mm at least.Because the linear molded contraction of compositions of thermosetting resin of the present invention is 3 to 5% approximately, be equivalent to linear molded contraction with rubber composition, in addition, by the integral body combination of resin part and silicon rubber part, and make the inevitable trouble that produces because of the molded contraction difference between two portions for example twist and not be out of shape and can take place.

In order to make this button top layer have enough physical strength with the falling weight impact test by describing in the back, suggestion is above-mentioned lower limit 0.5mm by the thickness of the molded button top layer of compositions of thermosetting resin of the present invention.When its thickness too hour, when falling weight, can form sometimes and break.In order to prepare this topped parts, consider the accuracy of gauge of metal die, the thickness of silastic-layer preferably arrives in the scope of 1mm 0.5.Requirement avoids compositions of thermosetting resin to mix and stir rubber composition with shaping, particularly lifting piece, because if not may obtain not meet the demands and inappropriate press button.

Rubber composition can be common preparing less than special requirement with by usual way.That is to say, by using for example mixing roll of a rubberized machine, kneader etc., with silicone rubber compound, solidifying agent and optional colorant and other additives mix fully, and thus obtained rubber composition are molded as in advance the so-called preform of for example sheet form with the suitable size that is suitable for molded operation and thickness.

This compositions of thermosetting resin is by with main component and the optional additive that comprises tinting material.Use a suitable mixing machine thorough mixing to prepare.This married operation can carry out all compositions together simultaneously, after perhaps preferably the mixing of free radical reaction solidifying agent being postponed till other compositions and having been formed uniform mixture in mixing machine.Requirement uses decompression to eliminate any bubble contained in flowable compositions of thermosetting resin before molded.

According to the present invention, the molding process of the topped parts of press button at first in the tapping hole of metal pattern by compositions of thermosetting resin molded button top layer, then by injection molding or compression molding and the moulded silicone rubber part realizes, even make and do not use any tackiness agent, resin part and silicon rubber part can both combine securely and integrally.Molding process illustrates in greater detail to 1E by accompanying drawing 1A.

As in 1A with vertical cross section explanation, the tapping hole of counterdie 3 is with air distributor or tubular pump (not showing on the figure), depresses the flowable compositions of thermosetting resin 2 of discharging from nozzle 1 and carries out filling adding.The flowable resin combination 2 that fills up the tapping hole of metal pattern 3 heats on the spot, implementing being cured to such degree, so that the top layer of this resin pool 2 lose flowability (seeing Figure 1B) at least.After this, shown in Fig. 1 C, the preformed board 4 of rubber composition is positioned on the counterdie 3, with the resin part 6 of topped solidified as the button top layer.Shown in Fig. 1 D, close up metal pattern with counterdie 3 and patrix 5, and keep high temperature in regulation in the long time like this, make rubber composition 4 mold pressings also solidify, to obtain the topped parts of press button, shown in Fig. 1 E, these topped parts are by this basic unit's part 10 when taking out from this metal mold, and lifting piece 9 and button push up basic unit 7 and be made up of this resin part 6 as the button top layer of compositions of thermosetting resin manufacturing of the present invention.

Rubber composition in the said procedure is molded and solidified by compression molding, but rubber composition is also can be by injection molding molded and solidify, and wherein rubber composition is being incorporated in the metal mold that is closed up by counterdie 3 and patrix 5 on the solidified resin part 6.

Molded and the condition of cure of compositions of thermosetting resin and rubber composition is decided by the type of each composition certainly, the size of product and other factors, and actual condition must be given definite earlier by giving the molded test of carrying out earlier.

In the compositions of thermosetting resin of the present invention, may be as described below by each composition role.That is to say, be suitable for binding resin part and silicon rubber part as the compound of the alkylene unsaturated polymerizable of component (b).Admittedly have the effect of the molded contraction that reduces resin combination as the Resins, epoxy of component (c), the physical strength to resin combination has improved action after curing simultaneously.The effect that has the solidification delay that prevents resin combination as the melamine resin of component (d), especially, with upper layer that air contacts in more obvious.As the free radical reaction solidifying agent of component (e) and as an acidic catalyst of component (f) respectively to the component (a) of unsaturated polyester resin with to the component (d) of melamine resin, play and guarantee the completely crued effect of resin combination.

Because above-mentioned each composition synergy, though compositions of thermosetting resin of the present invention need not any binding agent or base also can be on rubber composition molded and be solidified into and combine securely and intactly and form strong chemical bond.Because the principal constituent of resin combination is the unsaturated polyester resin as component (a), the resin combination after the curing does not have the flavescence shortcoming and very transparent, and it is painted to make that resin partly is easy to by required color.

Below, with by way of example some concrete scheme of the present invention is described, in advance by several tentative experiments to determine the suitable prescription of compositions of thermosetting resin of the present invention.The material that is used for the following describes amount term " umber " be meant " umber that weight is represented ".Tentative experiment 1

Resin combination is by unsaturated polyester resin (the Estar 1510C of 100 parts of weight as component (a), above-mentioned trade(brand)name) with 15 to 50 parts of weight as the phthalic acid diallyl ester of the undersaturated polymerizable compound of component (b) alkylene with as the compound and preparation of the solidifying agent of the free radical reaction of the different amounts of 2.5 parts of weight at the most (Niper BO, trade(brand)name) of component (e).Each resin combination is to be poured into (15mm diameter and 5mm are dark) in the metal pattern cast hole under 50 ℃ of temperature, and keeps therein motionless 1 minute, then with tweezers point contact pressure resin surface, solidifies situation to check the resin combination in upper layer.

Test-results is as follows.When not having component (e), then do not solidify.When the amount of component (b) be the amount of 20 or 35 parts of weight and component (e) when being 0.1 part of weight or when the amount of component (b) be the amount of 50 parts of weight and component (e) when being 2 parts of weight, then resin combination solidifies.When the amount of component (b) is the amount of 20 or 50 parts of weight and component (e) when being 2.5 parts of weight, then on the solidified surface of resin combination, the crack is arranged.Tentative experiment 2

Each all is by a basic composition with as commercial product (the Bnenmar G of the Resins, epoxy of 4 to 35 parts of weight of component (c) for a compositions of thermosetting resin, trade(brand)name) compound and the preparation, wherein, basic composition is by 100 parts of unsaturated polyester resins, the solidifying agent of 35 parts of phthalic acid diallyl esters and 1 part of free radical reaction is formed, each all as above-mentioned tentative experiment 1 employed identical.Each resin combination is poured under 150 ℃ of temperature in the rectangle pouring hole (20mm is long, and 15mm is wide and 5mm is dark) of metal pattern, and keeps there motionless 1 minute, to obtain solidified piece material, the piece material is carried out the measurement of linear molded shrinking percentage, represents with %.With the circular molded pouring hole (15mm diameter and 2mm are dark) of above-mentioned same resin combination filling additional metals mould and under same program curing curable resin composition and obtain the curing disk of resin combination, the shock test that this disk drops hammer by following described method.

The result of shock test is: when the amount of component (c) was 4 parts, this sample was not able to take the impact of the weight that falls from the 60cm height, and other samples can both withstand the impact of the weight that falls from the 200cm height.Molded contraction is measured the results are shown in following table 1.When the amount of component (c) was 35 parts of weight, owing to shrink very little, the cured block material can not take out in this rectangular molded aperture, makes molded linear shrinkage not measure.These results show that the amount of component (c) should be in 5 to 30 parts of weight ranges.

Table 1

Resins, epoxy, part weight 45 20 25 30

Molded shrinking percentage, the shock test that % 5.0 4.0 3.8 3.5 3.0 drops hammer

Fig. 2 A explanation is used for the device of shock test, and Fig. 2 B explanation is fallen axial, cross-sectional view on the sample with this device with weight.Straight tube 22 through 9.8mm in will having upwards erectly remains on the base table 21 to cover the sample 23 on basal plate 21.To have diameter 9.0mm and drift angle is the metal hammer 24 of 60 ° tapered lower end, and (having radius-of-curvature is the most advanced and sophisticated and heavy 4g of circle of 2.0mm) falls from high h (cm), to collide following sample, checks the impression or the crack that are occurred.When weight 24 from 200cm or lower part falls and do not detect when damage on sample 23, then this sample is just by the test as standard.Tentative experiment 3

Compositions of thermosetting resin each all (Cymel 303 with melamine resin product as the commercialization of 1 to 25 part of weight of component (d) by a basic composition, trade(brand)name) and as component (f) (Catalyst 4050 to an acidic catalyst of 2.5 parts of weight nearly, trade(brand)name) combination and the preparation, above-mentioned basic composition is the unsaturated polyester resin by 100 parts of weight, the benzene diformazan diallyl ester of 35 parts of weight, the Resins, epoxy of the solidifying agent of the free radical reaction of 1 part of weight and 25 parts of weight is formed, and wherein each is all employed identical with above-mentioned tentative experiment 2.Each resin combination all is injected under 150 ℃ of temperature in the rectangle pouring hole (45mm is long, and 20mm is wide and 7mm is dark) of metal pattern, keeps motionless 40 seconds therein to obtain solidified piece material.In addition, silicone rubber compound (KE951U by 100 parts of weight, the product of Shin-Etsu chemical company) and the solidifying agent (C-8 of 2 parts of weight, the product of above-mentioned company) preformed board of Zhi Bei rubber composition is put into covering the exposed surface of the cured resin piece material in this pouring hole, and at 200kgf/cm ²Pressure under close up molded 3 minutes of metal pattern to fill up the remaining space of pouring hole with molded and silicon rubber pressing mold, make solidified silicon rubber be attached to the surface of this resin component.Two portions complex body of Huo Deing takes out from metal pattern and checks and makes resin combination annotate silicon rubber part into by flowing and detect the curing situation of compositions of thermosetting resin like this.The inspection of component (d) and amount (f) and complex body the results are shown in following table 2.

Each illustrates a vertical cross section of thus obtained two part complex bodys Fig. 3 A and 3B, and this complex body is included in resin part 32 and the silicon rubber part 31 that interface 33A or 33B place combine.When compositions of thermosetting resin during with an acidic catalyst preparation of the melamine resin of 2 to 20 parts of weight and 0.1 to 2 part of weight, then as shown in Figure 3A, two portions 31, the 32nd, combine and resin combination 32 is not injected in the silicon rubber part 31 at a smooth and smooth interface 33A, and when the amount of these two compositions is not within above-mentioned scope, then shown in Fig. 3 B, interface 33B is not smooth and slick, but is wavy.The visual control result of Zhi Bei sample thus, be incorporated in the table 2, the wavy A that is divided in interface wherein, B, three grades of C with represent respectively the rips shape, in wavy and big wavy and solid state is divided into A, the expression completely solidified respectively that B and C are three grades, incomplete curing and do not solidify or solidify but have hole to form.

Table 2

The wavy interface solid state of melamine resin weight fraction an acidic catalyst

Parts by weight

1 0.1 C A

2 - B C

2 1 A A

10 2 A A

10 2.5 A C

20 0.1 A A

20 2 A A

25 1 A B tentative experiments 4

The result of above-mentioned tentative experiment 1 to 3 can be used as the selection of the screening formulation of compositions of thermosetting resin of the present invention, said composition comprises: the unsaturated polyester resin as component (a) of 100 parts of weight, the phthalic acid diallyl ester as component (b) of 35 parts of weight, the Resins, epoxy as component (c) of 25 parts of weight, the melamine resin as component (d) of 15 parts of weight, 1 part of weight as the solidifying agent of the free radical reaction of component (e) and an acidic catalyst as component (f) of 1 part of weight.

The piece material or the diameter that are shaped as 45mm * 20mm * 7mm are 15mm, thickness is the curing sample of the disk of 2mm, it is this compositions of thermosetting resin preparation that is called resin combination A by following, and be used for comparison, by following be called resin combination B and C by disclosed compositions of thermosetting resin on the open 6-3059988 and 660767 of Japanese Patent, the method for annotating by mould prepares.This resin combination B is that the dimethyl diphenyl silicone resin by 100 parts of weight mixes and prepares with the solidifying agent of 10 parts of weight and the curing catalysts of 0.4 part of weight, and resin combination C is by 2 of the ethylene glycol dimethacrylate of 100 parts of weight and 1 part of weight, 5-dimethyl-2,5-two (spy-butyl peroxy)-hexane preparation.

Sample is carried out the test of various physical propertiess aspect.These the results are shown in following table 3." guitar pick test (guitar pick test) " given in this table carried out as follows.The sample that is disc, with a medium-hard guitar pick, repeatedly impact in vertical direction, above-mentioned guitar pick is with a fixed frequency of fixed speed and 2 times/second, under 500 gram loads, reciprocally move up and down, till the surface at this sample at first detects damage or crack, and record impacts number of times.The resin combination A that provides in table 3, the test-results of B and C is equivalent to 3H respectively, the pencil hardness of H and F.

Table 3

Resin combination A B C

Solidification value, 140 180 165

Set time, 211

Molded shrinking percentage, % 3-4 34 7-8

Light permeable rate, % 85-90 65-70 85-92

Shock strength, cm 200 60 200

Shore D level hardness 85 80 55

Guitar pick test * 10 ⁴Inferior 30 25 10 tentative experiments 5

Curable rubber composition is to be mixed with by the solidifying agent of being recommended by the silicon rubber producer (D-8) of the silicone rubber compound of 100 parts of weight (KE 951U, the same) with 2 parts of weight.Employed resin combination A in above-mentioned tentative experiment 4, one of B and C carry out Unitarily molded in the metal pattern with a plurality of pouring holes that different size arranged, obtain the sample of two part complex bodys, as the button top layer mock partly of the topped parts of press button, it has the different thickness of the resin part shown in the following table 4 with different button top layer areas and with resin part and silicon rubber part button top layer total thickness partly.Shock test as shown in table 4, that sample drops hammer, the result under table 4IS title is divided into A and B secondary, represents height and low strength respectively.In table 4, time " C " is resin combination solidified is apparent to be finished and time to calculate second from being poured into, and the time " B " is that the silicone rubber resina composition reaches the good combination and the maximum ductile duration of pouring to assign to calculate from being poured between cured resin part and the silicon rubber part.

Table 4 (first part)

Button top layer size resin combination total thickness resin top layer A B C

Time time time time layer thickness area time time

mm ² IS C B IS C B IS C Bmm

mm2.3 0.3 5 B 10 10 B 10 60 B 10 22.3 0.5 5 A 10 10 B 10 60 A 10 22.3 2.2 5 A 10 10 B 10 60 A 10 23.5 2.5 5 A 10 10 B 10 60 A 10 23.5 0.9 5 B 10 10 B 10 60 B 10 210.0 7.0 5 A 10 10 A 10 60 A 10 210.0 9.0 5 A 10 10 A 10 60 A 10 225.0 17.5 5 A 15 10 A 15 60 A 15 225.0 23.8 5 A 15 10 A 15 60 A 15 22.3 0.4 20 B 10 10 B 10 60 B 10 22.3 1.1 20 A 10 10 B 10 60 A 10 22.3 1.5 20 A 10 10 B 10 60 A 10 23.5 2.5 20 A 10 10 B 10 60 A 10 23.5 3.3 20 A 15 10 A 15 60 A 15 210.0 7.0 20 A 15 10 A 15 60 A 15 210.0 9.5 20 A 20 10 A 20 60 A 20 225.0 17.5 20 A 20 10 A 20 60 A 20 225.0 23.8 20 A 20 10 A 20 60 A 20 22.3 1.0 150 A 20 10 B 20 60 A 20 22.3 1.8 150 A 20 10 B 20 60 A 20 2

Table 4 (second section) button top layer size resin combination total thickness resin layer top layer A B C

Time time time time thickness area time time

mm ² IS C B IS C B IS C Bmm

mm3.5 2.0 150 A 20 10 B 20 60 A 20 23.5 2.3 150 A 20 10 B 20 60 A 20 210.0 6.0 150 A 30 10 A 30 60 A 30 210.0 9.5 150 A 30 10 A 30 60 A 30 225.0 17.5 150 A 40 10 A 40 60 A 40 225.0 23.8 150 A 40 10 A 40 60 A 40 22.3 0.4 300 B 20 10 B 20 60 B 20 22.3 1.0 300 A 20 10 B 20 60 A 20 23.5 2.5 300 A 20 10 B 20 60 A 20 23.5 3.0 300 A 30 10 A 30 60 A 30 210.0 7.0 300 A 30 10 A 30 60 A 30 210.0 9.5 300 A 40 10 A 40 60 A 40 225.0 0.8 300 B 20 10 B 20 60 B 20 225.0 23.0 300 A 50 10 A 50 60 A 50 22.3 1.3 5000 A 200 10 B 200 60 A 200 22.3 1.8 5000 A 300 10 B 300 60 A 300 23.5 2.5 5000 A 300 10 B 300 60 A 300 23.5 3.3 5000 A 300 10 A 300 60 A 300 210.0 7.0 5000 A 400 10 A 400 60 A 400 210.0 9.0 5000 A 400 10 A 400 60 A 400 225.0 17.5 5000 A 600 10 A 600 60 A 600 225.0 23.8 5000 A 600 10 A 600 60 A 600 21

Flowable compositions of thermosetting resin of the present invention is by the unsaturated polyester resin (Polylite 8400) with 100 parts of weight, phthalic acid diallyl ester monomer (the Daisodap monomer of 40 parts of weight, the product of Daiso company), the Resins, epoxy of 40 parts of weight (Epolite 3002), the melamine resin of 15 parts of weight (Cymel 303), 0.5 the solidifying agent (Ni per BO) of the free radical reaction of part weight, 0.5 an acidic catalyst (Catalyst 4040) of part weight and the tinting material (BK-002-BP of 0.5 part of weight, portion's product by Novotek company), in a mixing machine uniform mixing 30 minutes and the preparation.

In addition, curable rubber composition is to prepare by roll-in by the solidifying agent of the free radical reaction of the silicone rubber compound of 100 parts of weight (KE951U) and 1 part of weight (Perhexa 3M), rubber composition is the plate that is molded as specific thickness in advance, and this plate cuts into specified dimension again.

As Figure 1A to the explanation of 1E, resin combination 2 is to advance in the pouring hole of counterdie 3 of metal pattern by air distributor nozzle 1 cast, and remain under 130 ℃, the patrix 5 that promotes by counterdie 3 tops is to fill pouring hole, and kept the topped parts of pressing mold press button therein 2 minutes to implement curable resin composition.After this, the plate 4 with the mold pressing in advance of rubber composition is placed on the counterdie to cover the exposed surface of solidified resin part 6, at 130 ℃ with at a 200kgf/cm ²Pressure under by closing up metal mold, and integral die 5 minutes, to implement the cure silicone rubber composition and it be attached on the surface of solidified resin part 6 to obtain the topped parts of integrally formed press button, it is by basic unit's parts 10, lifting piece 9, the cure silicone rubber part of button top layer 7 and the cured resin part 6 of button top layer are formed, and it is to take out from metal pattern 3,5.

Detect as visual method, it has good and acceptable outward appearance and non-yellowing to thus obtained topped parts on button top layer part, and this resin part and this silicon rubber interface between partly is smooth and slick and do not have a wave.When topped parts carry out tension test on automatic tension testing machine, topped parts are in silastic-layer internal cause adhesion defects and destroyed, rather than destroy because of the adhesion defects at the interface between resin part and the silicon rubber part, this bonding strength that is illustrated at the interface is very high.In addition, carry out repeatedly shock test by the button top layer that the button top basic unit of silicon rubber separates curable resin composition, find that its shock strength is very high with cutter cutting.

Embodiment 2

Flowable compositions of thermosetting resin of the present invention is by the unsaturated polyester resin (Rigolac) with 100 parts of weight, the Vinyl toluene of 40 parts of weight, the Resins, epoxy of 25 parts of weight (Epiol NPG-100), the melamine resin of 15 parts of weight (Cymel 232), thorough mixing prepares an acidic catalyst (Catalyst 4050) of the solidifying agent of the free radical reaction of 0.7 part of weight (Permek N) and 0.6 part of weight in mixing machine.

In addition, curable rubber composition is by the silicone rubber compound (KE951U) with 100 parts of weight, the solidifying agent of the free radical reaction of 1 part of weight (Perhexa 3M) and 5 parts of fine powder (SiplonB as light scattering agent, the product of Siplon Kasei company), prepare by roll-in, the rubber composition compressing tablet becomes the thickness of defined and cuts into the bar with specified dimension.

These resins and rubber composition are to be used for the photocon 41 of injection molding at the press button of dark place use, vertical cross section as shown in Figure 4, it comprises the photoconduction part 42 of transparent resin composition preparation and the scattering of light part of translucent silicone rubber preparation of compositions.Therefore, flowable compositions of thermosetting resin is poured in the pouring hole of metal pattern counterdie by air distributor under 140 ℃, and makes photoconduction part 42 and keep 45 seconds therein so that be cured.After metal pattern closes up, remain on that rubber composition in the supplies room of injector injects by one that nozzle is injected into the pouring hole of this metal pattern and at above-mentioned uniform temp and 180kgf/cm ²Pressure under solidified therein 5 minutes.

When the light guide member 41 of Huo Deing took out in metal pattern like this, having scattering of light parts 43 by the manufacturing of solidified silicon rubber and being had resiliently flexiblely, makes to be mounted on the press button plate and can be convenient to polytropy.Because the photoconduction part 42 by the resin combination manufacturing has very high transparency and good physical strength, so the thickness of this photoconduction part 42 may be little of 1mm or littler, so just make the total thickness of the topped parts of this press button reduce, and this little thickness of this photoconduction part 42 is to prepare with the silicone resin of conventional high rigidity.

Embodiment 3

Flowable compositions of thermosetting resin of the present invention is by the unsaturated polyester resin (Estar CL2170) with 100 parts of weight, the vinylbenzene of 50 parts of weight, the Resins, epoxy of 15 parts of weight (Light EsterDE), the melamine resin of 17 parts of weight (Cymel 701), an acidic catalyst (Catalyst 296-9) of the solidifying agent of the free radical reaction of 2 parts of weight (Permek V) and 0.9 part of weight mixes equably in mixing machine and prepares.

In addition, curable rubber composition is by the silicone rubber compound (MM3705, the product of Rhone-poulenc company) of 100 parts of weight and the solidifying agent (C-2) of 2 parts of weight are prepared by roll-in.

These resins and rubber composition are used for mold pressing cover plate 53, and as illustrated with axial section at Fig. 5, this cover plate 53 comprises the disk 51 of solidified resin combination and has the packing ring 52 of the silicon rubber of semi-circular cross-section.Therefore, be injected in the pouring hole of counterdie of metal pattern by the air distributor nozzle under 100 ℃ by top prepared flowable resin combination and make integrated disc portions, and keep 60 seconds therein to be cured.After this, rubber composition is expressed to the molded pouring hole that is used for the packing ring part from the extruding nozzle that is connected to ram pump, then metal pattern is closed up, at 100kgf/cm ²Pressure under compression moulding 5 minutes.Detect as visual, thus obtained two portions cover plate 53 has good surface appearance and is smooth and slick at the interface between the packing ring part 52 of the integrated disc portions 51 of solidified resin combination and cure silicone rubber composition.Integrated disc portions 51 have high physical strength and can go up any needed color, to satisfy aesthetic designing requirement.

Embodiment 4

Flowable compositions of thermosetting resin of the present invention is by the unsaturated polyester resin (Estar CO6001) with 100 parts of weight, the triallyl cyanurate of 43 parts of weight, the Resins, epoxy of 30 parts of weight (Blenmar G), the melamine resin of 30 parts of weight (Cymel 232), the solidifying agent of the free radical reaction of 2 parts of weight (Niper BMT-K40), tinting material (BK-0002-BP) thorough mixing in mixing machine of an acidic catalyst of 2 parts of weight (Catalyst 4050) and 3 parts of weight prepares.

In addition, curable rubber composition is by the silicone rubber compound (SE4705 with 100 parts of weight, the product of Toray Dow Corning company limited), solidifying agent (the PerbutylI of the free radical reaction of 1 part of weight, the product of Nippon grease company), tinting material (Color W-2 is by the product of Shin-Etsn chemical company) with 1 part of weight prepares by roll-in.This rubber composition is to be molded as the disk with a specified diameter and specific thickness in advance.

Is to be used to be molded in the pallet 64 that tray main body 62 bottoms that resin makes have rubber basic unit 63 as Fig. 6 with illustrated these resins of axial section (being added with cup 61 on it) and rubber composition.Therefore, flowable resin combination under 150 ℃, is poured into the mold pressing pouring hole of the metal mold that is used for tray body 62 by an air distributor nozzle, and keeps 3 minutes therein to be cured.After this, the rubber composition of this mold pressing in advance is incorporated in this metal mold, closes up this mould, at 200kgf/cm ²Pressure under, cure silicone rubber composition 4 minutes.The pallet 64 that takes out from metal mold is an integral body, and it comprises the basic unit of the tray main body 62 of the resin manufacture that combines and cure silicone rubber and need not insert wherein by any bonding coat.This rubber-based pallet 64 even be used on the shaky table of navigation ship and do not have the trouble of slip.Because the good combination between the tray main body 62 of resin manufacture and the rubber basic unit 63 aspect molded contraction, make pallet 64 not have bending or distortion and fabulous outward appearance is arranged.

Claims (3)

1, a kind of being suitable for is attached to the uniform compositions of thermosetting resin that cure silicone rubber is not partly inserted binder layer with method of moulding integral body, and said composition comprises following composition:

(a) unsaturated polyester resin of 100 parts of weight;

(b) compound of the alkylene unsaturated polymerizable of 20 to 50 parts of weight;

(c) Resins, epoxy of 5 to 30 parts of weight;

(d) melamine resin of 2 to 20 parts of weight;

(e) solidifying agent of the free radical reaction of 0.1 to 2 part of weight; With

(f) an acidic catalyst of 0.1 to 2 part of weight.

2, by the described uniform compositions of thermosetting resin of claim 1, it is characterized in that, be to be selected from vinylbenzene as the compound of the alkylene unsaturated polymerizable of component (b), Vinyl toluene, phthalic acid diallyl ester and cyanuric acid triallyl ester.

3, by the described uniform compositions of thermosetting resin of claim 1, it is characterized in that, be the superoxide that is selected from ketone as the solidifying agent of the free radical reaction of component (e); peroxy ketal; hydrogen peroxide, dialkyl peroxide, the organo-peroxide of diacyl peroxide and peroxyester.

Images