JP2737588B2 - Integrated molding of polypropylene resin and silicone rubber and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electric, electronic, automobile,
The present invention relates to an integrally molded article of a polypropylene-based resin and silicone rubber useful in the field of precision equipment and the like, and a method for producing the same.

[0002]

2. Description of the Related Art
Many methods for bonding an addition-curable silicone rubber and an organic resin have been proposed. For example, a method is known in which a primer is applied to the surface of a molding resin, an uncured silicone rubber material is applied thereon, and this is cured and bonded, or a method in which a self-adhesive silicone rubber material is cured from the top of the molding resin. ing. With respect to this self-adhesive silicone rubber material, many proposals have been made especially for its adhesive component.

[0003] Further, a method of adding an organohydrogenpolysiloxane containing 30 mol% or more of hydrogen atoms directly bonded to silicon atoms to an organic resin and bonding the resultant to an addition-curable silicone rubber composition (Japanese Patent Publication No. 2-34311). Integration of Silicone Rubber into Organic Resin by Physical Fitting Method (JP-B-63-45292), Silicone Rubber Composition on Olefin Resin Grafted with Compound Having Aliphatic Unsaturation Group and Silicon-Atom-Hydrolysable Group (Japanese Unexamined Patent Publication (Kokai) No. 63-183843), and a thermoplastic resin and a silicone to which a compound containing an unsaturated group and a hydrogen atom directly bonded to a silicon atom are added as proposed by the present inventors. A method of bonding and integrating a rubber composition has also been proposed.

[0004] However, the method of bonding using a primer requires time and effort to take out the resin molded product once molded from a mold or the like and apply the primer.

On the other hand, a self-adhesive addition-curable silicone rubber material does not have a sufficient adhesive strength to a polypropylene resin under the conditions used as an integral molded product.

Further, among the above proposals, the method of adding an organohydrogenpolysiloxane to an olefin resin may cause a change in the properties of the resin itself due to the addition of the siloxane, making it difficult to obtain the original properties of the resin. is there. Also, the method of integrating by physical fitting, there is a possibility that the fitting may be released by physical force, the olefin resin grafted with a compound having an aliphatic unsaturated group and a silicon atom bond hydrolyzable group. The method used has the disadvantage that a primer is required for the integration of the addition-curable silicone rubber.

On the other hand, in recent years, silicone rubber has been recognized for its high reliability in heat resistance, weather resistance, electric characteristics and the like, and its use is expanding in electric / electronic fields, automobile fields, and the like. It has been desired to supply an integrally molded body in which a polypropylene resin and a silicone rubber are firmly bonded.

SUMMARY OF THE INVENTION The present invention has been made in order to meet the above-mentioned demands. It is intended that a polypropylene resin or a composition containing the resin and a silicone rubber be bonded to each other with sufficient adhesive strength to withstand practical use. An object of the present invention is to provide an integrated molded article of a silicone resin and a silicone resin, which is capable of easily and reliably producing such an integrally molded article with silicone rubber in a short time, and which can be injection-molded. And

[0009]

The present inventors have conducted intensive studies to achieve the above object, and as a result, as a polypropylene resin, specific aliphatic unsaturated groups of (1) to (3) described later. And (I) having at least one hydrogen atom directly bonded to a silicon atom in one molecule, and a silicone rubber bonded to and integrated with the polypropylene resin. A silyl group, a glycidyl group, a compound containing one or more groups selected from acid anhydride groups, or [II] having at least one hydrogen atom directly bonded to a silicon atom in one molecule, And a divalent — (CR ¹ R ² ) _n — bond, where n is an integer of 2 to 30, R ¹ and R ² are a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon having 1 to 10 carbon atoms. Is the base) By using an addition-curable silicone rubber containing a compound containing, the adhesive strength of an addition-curable silicone rubber composition is low or the adhesive strength that can sufficiently withstand polypropylene resin that could not be bonded in a short time. And a molded article of silicone rubber having
When the silicone rubber composition containing the compound of the formula (I) is used, it adheres sufficiently to the polypropylene resin under a short curing condition by using an injection molding method, and the silicone rubber itself is sufficiently removed from a molding die. It has been found that a polypropylene / silicone rubber integrally molded product which has never been peeled off with practicality can be obtained.

That is, the present invention provides: (1) a random copolymer obtained by randomly copolymerizing a non-conjugated diene compound represented by the following general formula (1) with propylene; (3) a graft copolymer obtained by graft-polymerizing a diene compound represented by (2), and (3) as a first step, block copolymerizing a monomer compound having both an unsaturated bond and a functional group with propylene, or Graft polymerization of polypropylene by a radical method, followed by reaction with a compound having a functional group that reacts with a functional group and having an unsaturated bond as a second step, and an aliphatic selected from a modified polypropylene having an unsaturated bond introduced into the polypropylene. A polypropylene resin having an unsaturated bond or a composition containing the resin has the following [I] or [I
An integrated molded article of a polypropylene-based resin and a silicone rubber, wherein the addition-type silicone rubber containing the compound of I) is integrated;
(A) an alkenyl group-containing organopolysiloxane, (b) a hydrogen atom directly bonded to a silicon atom is added to a polypropylene-based resin having an aliphatic unsaturated bond selected from (3) or a molded product of a composition containing the resin. Contacting at least two organohydrogenpolysiloxanes in the molecule, (c) a catalyst for addition reaction, and (d) a silicone rubber composition containing the following compound (I) or (II): Alternatively, there is provided a method for producing an integrally molded article of a polypropylene resin and silicone rubber, wherein the silicone rubber composition is cured at a temperature lower than the softening temperature of the composition containing the resin. [I] A compound having at least one hydrogen atom directly bonded to a silicon atom in one molecule and containing one or more groups selected from an alkoxysilyl group, a glycidyl group and an acid anhydride group. [II] One molecule has at least one hydrogen atom directly bonded to a silicon atom, and is a divalent-(CR ¹ R ² ) _n -bond (where n is an integer of 2 to 30, R ¹ and R ² is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms). Further, the present invention provides a polypropylene-based resin comprising an addition type silicone rubber containing a compound of the above [II] integrated with a polypropylene-based resin having an aliphatic unsaturated bond or a composition containing the resin. (A) an alkenyl group-containing organopolysiloxane, and (b) a silicon atom directly bonded to an integrally molded article of a resin and a silicone rubber, and a molded article of a polypropylene resin having an aliphatic unsaturated bond or a composition containing the resin. Contacting an organohydrogenpolysiloxane having at least two hydrogen atoms in one molecule, (c) a catalyst for an addition reaction, and (d) a silicone rubber composition containing the compound of the above [II]. Curing the silicone rubber composition at a temperature lower than the softening temperature of the resin or a composition containing the resin. That provides a method for manufacturing a integrally molded body of the polypropylene resin and the silicone rubber.

Hereinafter, the present invention will be described in more detail. The polypropylene resin used in the present invention contains an aliphatic unsaturated group, and examples of such a polypropylene resin include the following (1) to (3). Further, as the composition containing the polypropylene resin,
Examples shown in (4) are given. However, a random copolymer of propylene and a diene having a structure of CH ＝ C (CH ₃ ) ₂ has poor adhesion and is not suitable for use in the present invention. (1) Propylene randomly copolymerized with a non-conjugated diene compound represented by the following general formula

[0012]

Embedded image (Where R _{1 to} R ₄ are a hydrogen atom or an alkyl group,
Not have the structure of _{-CH = C (CH 3) 2} , thus R _1, R ₂ is a methyl group, R ₃ do not represent simultaneously a hydrogen atom. n shows the integer of 1-20. )

As such a non-conjugated diene, for example, 2-
Methyl-1,4-pentadiene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 1,4-heptadiene, 4-methyl-1,4-hexadiene, 4-methyl-1,4-heptanediene , 4-ethyl-1,4-
Heptadiene, 1,5-heptadiene, 1,5-octadiene, 5-methyl-1,5-heptadiene, 2-methyl-1,5-hexadiene, 1,6-octadiene, 6
-Methyl-1,6-octadiene, 2-methyl-1,6
-Heptadiene, 1,9-decadiene, 1,13-tetradecadiene and the like. In addition, cyclic non-conjugated dienes such as vinylcyclohexene, vinylnorbornene, dicyclopentanediene, and ethylidene norbornene, and toluenes such as 1,3,7-octatriene and 1,5,9-decatriene can also be used. . Among these, 1,9-decadiene, 1,13-tetradecadiene and the like are particularly preferable. These non-conjugated diene compounds have two
A mixture of two or more species can be used.

For random copolymerization of propylene and a non-conjugated diene compound, a conventional copolymerization method using a Ziegler-Natta catalyst may be applied. In this case, the ratio of the non-conjugated diene is desirably 0.01 to 20 mol%. A more preferred content of the non-conjugated diene is 0.05 to 15 mol%. More preferably, the content of the non-conjugated diene is 0.1 to 10 mol%. When the content of the non-conjugated diene is less than 0.01 mol%, a strong adhesive force with the silicone rubber cannot be obtained. If it exceeds 20 mol%, the crystallinity of the copolymer will be significantly reduced.

Other unsaturated compounds such as ethylene and butene-1 may be copolymerized with the random copolymer. The melt flow rate of this copolymer (MFR 23
0 ° C., 2.16 kg load) is usually 0.01 to 1000
g / 10 min is appropriate. Further, different kinds of polyolefins may be blended with the random copolymer. (2) Graft copolymer obtained by graft-polymerizing a diene compound represented by the following general formula to polypropylene

[0016]

Embedded image (However, R _{1 to} R ₄ are a hydrogen atom or an alkyl group, and m
Represents an integer of 0 to 20. )

Examples of the diene include 1,3-butadiene, 2-methyl-1,4-pentadiene, 1,4
-Hexadiene, 4-methyl-1,4-hexadiene,
4-methyl-1,4-heptadiene, 4-ethyl-1,
4-heptadiene, 1,5-heptadiene, 1,5-octadiene, 5-methyl-1,5-heptadiene, 2-
Methyl-1,5-hexadiene, 1,6-octadiene, 6-methyl-1,6-octadiene, 2-methyl-
1,6-heptadiene, 1,9-decadiene, 1,13
-Tetradecadiene and the like. In addition, cyclic non-conjugated dienes such as vinylcyclohexene, vinylnorbornene, dicyclopentanediene, and ethylidene norbornene, and toluenes such as 1,3,7-octatriene and 1,5,9-decatriene can also be used. . Among these, 1,9-decadiene, 1,13-tetradecadiene and the like are particularly preferable. These non-conjugated diene compounds can be used as a mixture of two or more kinds.

In order to graft a diene onto a polypropylene by a radical method, the polypropylene is dissolved in an organic solvent such as xylene or toluene, and a diene and a radical generator are added to the solution to react. Any method can be used, such as a melt-kneading method in which a compound, a diene and a radical generator are melt-kneaded and reacted. In this case, the ratio of the diene is 0.01 to 2
It is desirable that the content be 0 mol%.

As the radical generator (reaction initiator),
For example, benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, acetyl peroxide, tert-butyl peroxypivalate, 2,5-dimethyl-2,5
Peroxides such as di-tert-butyl peroxyhexine and t-butyl peroxy perbenzoate; and diazo compounds such as azobisisobutyronitrile are preferred. The mixing ratio of the monomer 1 having an unsaturated bond
The range of 1 to 50 parts by weight relative to 00 parts by weight is desirable.
The MFR of this graft copolymer is usually 0.01 to 10
It is suitably set to 00 g / 10 min. Further, different polyolefins may be blended with the graft copolymer. (3) As a first step, a monomer compound having both an unsaturated bond and a functional group is block-copolymerized with propylene, or graft-polymerized to a polypropylene by a radical method, and then reacted with a functional group as a second step. Modified polypropylene obtained by reacting with a compound having a functional group and having an unsaturated bond to introduce an unsaturated bond into polypropylene.

The compound used as the first step includes, for example, unsaturated amide or unsaturated amine such as acrylamide, methacrylamide, allylamine, glycidyl methacrylate, glycidyl acrylate, glycidyl allyl ether, N- [4- (2,3-epoxy Unsaturated epoxy compounds such as propoxy) -3,5-dimethylbenzyl] acrylamide, unsaturated carboxylic acids such as maleic anhydride, hymic anhydride, and acrylic acid; unsaturated compounds having a hydroxyl group such as vinyl oxazoline compounds and allyl alcohol; Is mentioned. In order to block copolymerize propylene and the above compound having an unsaturated bond, a living polymerization method may be applied (Japanese Patent Application Laid-Open No. 60-25261).
No. 4). In this case, the ratio of the compound introduced into the produced polypropylene copolymer is 0.01 to 20 mol%.
Is preferred. The copolymer may be copolymerized with another unsaturated compound such as ethylene butene-1. The MFR of this copolymer is usually 0.01 to 1000 g / 1.
0 min is appropriate.

In order to graft the above compound having an unsaturated bond to polypropylene by a radical method, the polypropylene is dissolved in an organic solvent such as xylene or toluene, and the above compound and a radical generator are added to the solution to react. Solution, extruder, etc.
Any method such as a melt-kneading method in which the compound and the radical generator are melt-kneaded and reacted can be used. In this case, the content of the above compound is desirably 0.01 to 20 mol%.

As the radical generator (reaction initiator),
For example, benzoyl peroxide, lauroyl peroxide, ditertiary butyl peroxide, acetyl peroxide, tertiary butyl peroxybenzoic acid, dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, tertiary butyl peroxypivalate, 2,5-dimethyl- Peroxides such as 2,5-di-tert-butylperoxyhexine and t-butylperoxyperbenzoate and diazo compounds such as azobisisobutyronitrile are preferred. The mixing ratio is preferably in the range of 1 to 50 parts by weight based on 100 parts by weight of the compound having an unsaturated bond. The MFR of this graft copolymer is usually 0.01 to 1000 g / 10 m
It is appropriate to use in.

The compound used in the second step may be a compound different from the compound used in the first step.

In the reaction of the second step, the polypropylene prepared in the first step is dissolved in an organic solvent such as xylene or toluene, and the above compound is added to the solution, and the reaction is carried out by a solution method, an extruder, or the like. Any method such as a melt kneading method in which the polypropylene prepared in the first stage and the above compound are melt-kneaded and reacted can be used.

It is appropriate that the MFR of the polypropylene having the unsaturated bond introduced is usually 0.01 to 1000 g / 10 min. Further, different types of polyolefins may be blended with this polypropylene. (4) A resin composition obtained by blending any of the following (i) to (iii) with ordinary polypropylene. In this case, two or more types can be used in combination. (I) Modified polypropylene (including oligomers) of (1) to (3) above. (Ii) Polymers and oligomers having an unsaturated bond in the molecule. For example, ethylene-propylene-diene rubber using ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene or the like as a diene, butadiene-based copolymer, 1,2-polybutadiene, terminal double-bonded polyolefin and the like can be mentioned. (Iii) Silica, GF, etc. surface-treated with a silane coupling agent having an unsaturated bond in the molecule. Such silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2
Silane coupling agents having an unsaturated bond such as -methoxyethoxy) silane and 3-methacryloxypropyltrimethoxysilane.

On the other hand, the silicone rubber integrated with the polypropylene resin or the composition containing the resin is an addition type silicone rubber.
(A) an alkenyl group-containing organopolysiloxane,
(B) an organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to silicon atoms in one molecule, (c) a catalyst for an addition reaction, and (d) a compound of the following [I] or [II]. A cured silicone rubber composition is preferred.

As the alkenyl group-containing organopolysiloxane of the component (a), a known organopolysiloxane which is usually used as a main raw material of an addition-curable silicone rubber composition can be used. Those having a viscosity of 100 cp to 100,000 cp at room temperature are preferred.

In particular, as this organopolysiloxane, those represented by the general formula R _a SiO _{(4-a) / 2} are preferably used. In this formula, R is a substituted or unsubstituted monovalent hydrocarbon group, preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms. Specifically, alkyl groups such as methyl, ethyl and propyl; alkenyl groups such as vinyl, propenyl and butenyl; aryl groups such as phenyl and xylyl;
Halogen-substituted such as -trifluoropropyl, and a cyano-substituted hydrocarbon group. The monovalent hydrocarbon groups may be different from each other or the same, but it is necessary that the molecule contains an alkenyl group. in this case,
The amount of the alkenyl group in R is preferably 0.01 to 10 mol%, particularly preferably 0.1 to 1 mol%. Here, a is in the range of 1.9 to 2.4, and the organopolysiloxane may be linear or branched including RSiO _3/2 units or SiO _4/2 units. Good. The substituent of the silicon atom may be basically any of the above, but it is preferable to introduce a vinyl group as the alkenyl group and a methyl group or a phenyl group as the other substituent.

Examples of such an organopolysiloxane include the following.

[0030]

Embedded image (R has the same meaning as described above (excluding an aliphatic unsaturated group), and m and n are m + n = 100-5000, n = 1
00-5000, m / (n + m) = 0.001-0.1
It is. )

The organopolysiloxane can be produced by a method known to those skilled in the art. For example, these production methods can be obtained by performing an equilibration reaction between an organocyclopolysiloxane and a hexaorganodisiloxane in the presence of an alkali or acid catalyst.

The organohydrogenpolysiloxane of the component (b) reacts with the component (a) and acts as a crosslinking agent, and its molecular structure is not particularly limited. Various types such as cyclic and branched structures can be used, but it is necessary that one molecule contains a hydrogen atom directly bonded to at least two silicon atoms. Substituents bonded to silicon atoms other than hydrogen in this compound are the same as the substituents in the organopolysiloxane of the component (a). The added amount of the component (b)
0.4 with respect to one alkenyl group contained in the component (a).
５5 equivalents, preferably in the range of 0.8-2 equivalents. If the amount is less than 0.4 equivalent, the crosslink density becomes too low and adversely affects the heat resistance of the cured silicone rubber. If the amount is more than 5 equivalents, a problem of foaming due to a dehydrogenation reaction may occur, or the heat resistance may be adversely affected.

This can be obtained by a production method known to those skilled in the art. For example, a very common production method is hexamethyldisiloxane or 1,1-dihydro-2,2,3,3- which can be an end group with octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane. A compound containing a teratomethyldisiloxane unit can be easily obtained by equilibrating at a temperature of about -10 to + 40 ° C in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid, or methanesulfonic acid.

Examples of the catalyst for the addition reaction of the component (c) include platinum and a platinum compound, and these promote the curing addition reaction (hydrosilation) between the component (a) and the component (b). Used as a catalyst, which may be known to those skilled in the art. Accordingly, examples thereof include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, and complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols and the like. Also, a rhodium complex or the like can be used. Incidentally, the amount of addition may be appropriately increased or decreased according to the desired curing speed,
Usually, the amount of platinum or rhodium is 0.1 to the component (a).
The range may be 1 to 1000 ppm, preferably 1 to 200 ppm.

The component (d) used in the present invention is a compound of the following [I] or [II], that is, [I] having at least one hydrogen atom directly bonded to a silicon atom in one molecule, and A compound containing one or more groups selected from an alkoxysilyl group, a glycidyl group and an acid anhydride group [II] a molecule having at least one hydrogen atom directly bonded to a silicon atom in one molecule; -(CR ¹ R ² ) _n -bond (where n is an integer of 2 to 30, R ¹ and R ² are a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms) ).

The minimum required property of the component (d) is that the molecule contains at least one hydrogen atom directly bonded to a silicon atom in the molecule, and improves the affinity for an organic resin (modified polypropylene resin) to be bonded. That is. here,
From the viewpoint of bonding the silicone resin itself to the organic resin to be bonded, it is more preferable to have two or more hydrogen atoms directly bonded to silicon atoms.

For such purposes, many of the conventionally proposed adhesion-imparting components fall under this category. However, when conventional polypropylene was used, sufficient adhesiveness could not be obtained even when these adhesiveness-imparting components were used. On the other hand, the polypropylene resin to be bonded according to the present invention contains an unsaturated group capable of hydrosilylation, and can sufficiently withstand practical use even with a polypropylene resin that was poor in practical adhesiveness in the conventional method. This is to provide adhesiveness.

As the component (d), the above [I]
The following are examples of the compound [I].

[0039]

Embedded image

[0040]

Embedded image

However, such a compound is represented by (d)
When used as a component, although sufficient adhesive strength can be obtained, when silicone rubber is to be molded into a certain shape, when a metal molding jig such as a mold is used, it is bonded to this molding jig. It has the drawback that it will. The method of using a material with poor adhesiveness such as applying a Teflon resin coat to the molding jig most is also one means of solving the problem, but it may lack reliability in terms of service life, etc. Also, it cannot be used when the precision of the molded product surface is important.

In such a case, the above-mentioned adhesive functional groups such as trialkoxysilyl group, glycidyl group,
Compounds having no groups such as acid anhydride groups are useful. However, this does not apply to the case where the reactivity is sufficiently suppressed by the steric restraint or electronic action of the substituent or the surrounding group even if it has the above group. Examples of such compounds include the compounds of the above [II], and the following compounds can be exemplified.

[0043]

Embedded image

The amount of the component (d) is as follows:
It is preferably 0.05 to 10 parts by weight based on 00 parts by weight.

When the physical strength of the silicone rubber is required in the present invention, finely divided silica is used. In this case, finely divided silica having a specific surface area of 50 m ² / g or more is useful. Examples of such materials include Aerosil 130, 200, 30 as hydrophilic silica.
0 (Nippon Aerosil, Degussa), Cab
osil MS-5, MS-7 (Cabot), R
and Herosil QS-102, 103 (manufactured by Tokuyama Soda Co., Ltd.) and Nipsil LP (manufactured by Nippon Silica Co., Ltd.). Also, as the hydrophobic silica, Aerosil
R-812, R-812S, R-972, R-974
(Made by Degussa), Rheosil MT-
10 (manufactured by Tokuyama Soda Co., Ltd.) and Nipsil SS series (manufactured by Nippon Silica Co., Ltd.).

When it is necessary to adjust the curing time in order to put these materials into practical use, when a control agent is used, a vinyl group-containing organopolysiloxane such as vinylcyclotetrasiloxane, triallyl isocyanurate, alkyl maleate is used. And compounds selected from the group consisting of acetylene alcohols and their silanes, modified siloxanes, hydroperoxides, tetramethylethylenediamine, benzotriazole and mixtures thereof.

Further, non-reinforcing fillers such as quartz powder, diatomaceous earth and calcium carbonate, inorganic pigments such as cobalt blue,
It is also possible to add a coloring agent such as an organic dye, and a heat-resistant and flame-retardant improver such as cerium oxide, zinc carbonate, manganese carbonate, red iron oxide, titanium oxide and carbon black.

As a method of integrally molding an uncured addition type silicone rubber composition having such a composition on a propylene resin, an uncured addition type silicone rubber composition is formed on a pre-molded polypropylene resin. A method in which the composition is placed in a desired shape and heated at a temperature not higher than the temperature at which the polypropylene-based resin softens (die, coating, dipping, etc.), and an uncured addition silicone on a pre-formed polypropylene-based resin Heat the rubber composition at a temperature below the temperature at which the polypropylene resin softens,
A compression method, a method in which a polypropylene-based resin is first injection-molded into a mold by an injection molding machine, and then a method of heating and injecting the addition type silicone rubber composition into the mold are exemplified.

In this case, as a method for producing a molded article of the unsaturated group-containing polypropylene resin, a usual thermoplastic resin molding method is applied. As an example of such a method, for example, the polypropylene resin is pelletized,
A known method is convenient in which a mold is poured into a mold heated to a temperature higher than the softening point of the polypropylene resin, and then the mold is cooled to a temperature lower than the softening point of the polypropylene resin. In this case, an apparatus generally called an injection molding machine or a transfer molding machine can be used. Next, the silicone rubber composition to be molded on the polypropylene resin molded article may be in a liquid state in an uncured state, putty-like, or paste-like. The so-called liquid or paste-like thing is desirable.

[0050]

The integrated molded article of the polypropylene resin and the silicone rubber of the present invention comprises the above-mentioned (1)-(3) polypropylene resin containing an aliphatic unsaturated group or a composition containing the resin. The addition type silicone rubber containing the compound of the above [I] or [II] is used, and is laminated, adhered and integrated, so that a molded article in which the polypropylene resin and the silicone rubber are firmly adhered is obtained. be able to. For this reason, this molded article is effectively used for parts such as electric, electronic, automobile, and precision equipment, and can effectively exhibit the properties of the polypropylene resin and the silicone rubber.

Further, according to the production method of the present invention, an integrally molded article of such a polypropylene resin and silicone rubber can be easily and reliably produced, and particularly, molding of a molded article of a polypropylene resin or a composition containing the resin. In addition to allowing the silicone rubber composition to be brought into contact with the molded product by injection molding, in this case, if the compound of the above [II] is used as the component (d), the silicone rubber can be removed at the time of demolding. It peels off smoothly from the mold and hardly adheres to the mold.

[0052]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Example 1 Preparation of Adhesive Silicone Rubber Composition 100 parts by weight of a dimethylsiloxane polymer having a viscosity of 10,000 centipoise at 25 ° C. and both ends blocked with a dimethylvinylsilyl group, 100 parts by weight, and a specific surface area of 300 cm ^Two
/ G of fumed silica, 8 parts by weight of hexamethyldisilazane, and 1 part by weight of water were charged into a kneader, stirred and mixed at room temperature for 1 hour, and then heated to 150 ° C. and kept at room temperature for 2 hours. Was done. Thereafter, the mixture is cooled to room temperature,
In addition to this, both ends are blocked with a dimethylvinylsilyl group.
20 parts by weight of a dimethylsiloxane polymer having a viscosity of 10,000 centipoise at 5 ° C., 3 parts by weight of a methylhydrogenpolysiloxane having a viscosity of about 10 centipoise at room temperature represented by the formula (A), and silicon atom 4 parts by weight of a vinylmethylpolysiloxane having a viscosity of 1,000 centipoise at room temperature containing 5 mol% of a vinyl group directly bonded to, 0.1 part by weight of acetylene alcohol to extend the time until curing at room temperature, 50 ppm of a platinum vinyl siloxane complex as a platinum atom was added and mixed well until uniform, to obtain a liquid addition type silicone rubber composition (I).

[0054]

Embedded image The mechanical properties when a sheet was prepared from this composition (I) by pressing under the curing conditions of 120 ° C./10 minutes were as follows. Hardness (JIS A) 40; Elongation 500%; Tensile strength 100 kgf / cm ² ; Tear strength 35 kgf / c
m

Next, 2 parts by weight of a compound represented by the following formula (B) or (C) (component (d) of the present invention and an adhesion-imparting component) were added to 100 parts by weight of the composition (I). An adhesive silicone rubber composition according to the invention was prepared.

[0056]

Embedded image

Preparation of Polypropylene Resin Propylene and 1,9-decadiene were randomly copolymerized at 70 ° C. using a Ziegler-Natta catalyst, a propylene polymerization catalyst containing titanium trichloride as a main component. The 1,9-decadiene content of the obtained random copolymer was determined by NMR.
Was 1.5 mol%. Also, MFR
Was 0.3 g / 10 min.

Next, the above-mentioned modified polypropylene resin was put into a thermoplastic resin injection molding machine, plasticized at 200 ° C., and then injected into a multi-cavity sheet-type mold cavity to obtain a thickness of 2 mm × width of 25 mm × length. Several 100 mm long sheets were obtained. The injection conditions were: injection time 6 seconds, cooling time 30
Seconds, injection pressure 1000 kg / cm ² , mold clamping pressure 35 to
n, the cavity temperature was 60 ° C.

Next, the prepared sheet, chrome-plated metal, nickel-plated metal and aluminum alloy of the same dimensions were fixed to a jig for preparing a tensile shear adhesion test piece, and an appropriate amount of the above-mentioned adhesive silicone rubber composition was poured into the jig. , 120
The composition was cured by heating in a constant temperature bath for 8 minutes. Using the test piece of FIG. 1 thus obtained, the adhesiveness was examined. Table 1 shows the results. In FIG. 1, a is a polypropylene resin or metal specimen, b is a cured product of a silicone composition (2 × 25 × 100 mm), c is an adhesive portion, and d and e.
Is a support.

[Comparative Example 1] The modified polypropylene resin was changed to an unmodified polypropylene resin, and under the same injection molding conditions as in Example 1, the thickness was 2 mm × width 25 mm × length 100 m.
Several m sheets were obtained. Further, the liquid addition-type silicone rubber composition prepared in Example 1 was mixed with 120
Heating was carried out for 8 minutes in a constant temperature bath at ℃ to prepare an adhesion test piece shown in FIG. 1 and the adhesion was examined. Table 1 shows the results.

[0061]

[Table 1]

Example 2 Modified polypropylene resin sheet (thickness 2 mm × width 25 mm × length 100 mm) using the same resin and the same injection molding method and conditions as in Example 1
Several were obtained.

Next, the sheet, the chromium-plated metal, the nickel-plated metal and the aluminum alloy of the same size were fixed to a jig for preparing a tensile shear adhesion test piece, and 100 parts by weight of the liquid addition type silicone rubber composition (I) was obtained. An appropriate amount of an adhesive silicone rubber composition containing 0.5 and 1 part by weight of a compound represented by the following formula (D) or (E) was poured into the same jig, and the mixture was placed in a 120 ° C constant temperature bath for 8 minutes. Heated to cure. Using the test piece of FIG. 1 thus obtained, the adhesiveness was examined. Table 2 shows the results.

[0064]

Embedded image

Comparative Example 2 Modified polypropylene resin (without filler) was replaced with unmodified polypropylene resin (without filler)
To 2 mm in thickness under the same injection molding conditions as in Example 1.
Several sheets having a width of 25 mm and a length of 100 mm were obtained. The liquid addition-type silicone rubber composition (I) prepared in Example 1 was heated and cured in a thermostat at 120 ° C. for 8 minutes on the prepared sheet, and an adhesion test piece shown in FIG. 1 was prepared. .
Table 2 shows the results.

[0066]

[Table 2]

[Embodiment 3] The molding machine used in this embodiment is a two-color injection molding machine equipped with two injection devices. As shown in FIG. 2, the nozzles (1) and ( 2) The cavities (5) of the molds (3) and (4)
Connect to (6). The nozzle (1) is ejected from the mold parting line, and the nozzle (2) is ejected from the center of the right side of the mold. The mold used was the left mold piece (3)
And a right mold piece (4). Molding recesses are formed at two locations on each of the opposing surfaces, and the cavity portions (5) and (5) are formed by the molding recesses as shown in FIG. 6) is formed (see FIG. 2).

First, the same polypropylene resin as in Example 1, which had been modified with a diene compound by 1.5 mol%, was charged into the injection molding apparatus, melted at 200 ° C., and passed through the nozzle (1) to the cavity (5). ) To form a resin sheet molded product (7). The conditions are: injection time 6 seconds, cooling time 35 seconds, cavity (5) and left mold piece (3).
Was 60 ° C. (see FIG. 3).

Next, the right mold piece (4) is removed, the mold is opened, and the resin sheet molded body (7) is held in the concave portion of the left mold piece (3). ) Is rotated 180 °, the right mold piece (4) is aligned, and the mold is clamped again.
The cavity for forming the silicone rubber sheet molded product was formed by the surface formed in the resin sheet molded product (7) and the molding concave surface of the mold piece (4) (see FIG. 4).

In this state, 100 parts by weight of the liquid addition type silicone rubber composition (I) was applied to the surface formed on the resin sheet molded product (7) from the nozzle portion (2) of the injection device.
The composition obtained by adding 0.5 and 1 part by weight of the compounds (D) and (E) used in the above was injected to form a molded rubber sheet (8). The conditions were an injection time of 6 seconds and a curing time of 100.
In seconds, the temperature of the left mold piece (3) was 60 ° C., and the temperature of the right mold piece (4) was 80 ° C. (see FIG. 5).

By the above manufacturing steps, a composite molded body composed of a resin sheet and a rubber sheet as shown in FIG. 6 (width 2.5 mm, length 15 cm, thickness 2 mm, resin and silicone rubber are the same size) I got The composite molded products of the compositions to which 0.5 and 1 part by weight of the compounds (D) and (E) used in Example 2 were added were all firmly adhered, and had good dimensional accuracy and productivity. Was. The chrome-plated carbon steel mold and rubber sheet were all easily peeled off.

Comparative Example 3 The composite of FIG. 6 was prepared by the same injection molding method and conditions except that the modified polypropylene resin of Example 3 was changed to an unmodified polypropylene resin, and the adhesion was examined. And the silicone rubber peeled off easily.

[Brief description of the drawings]

1A and 1B show an adhesion test piece, wherein FIG. 1A is a front view and FIG. 1B is a plan view.

FIG. 2 is a schematic sectional view of an injection molding machine used for molding a molded article of the present invention.

FIG. 3 is a schematic sectional view of a state where a polypropylene resin is injection-molded in the molding machine.

FIG. 4 is a schematic cross-sectional view of the molding machine in a state where a mold portion is inverted.

FIG. 5 is a schematic sectional view of a state where the silicone rubber composition is injection-molded in the same state.

6 is a perspective view of a molded body obtained after the operation of FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Nozzle part 2 Nozzle part 3 Mold piece 4 Mold piece 5 Cavity part 6 Cavity part 7 Polypropylene resin sheet molding 8 Silicone rubber sheet molding

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // B29K 23:00 83:00 (72) Inventor Akira Matsuda 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma 1-10 Shin-Etsu Chemical Co., Ltd. (72) Inventor Yasushi Yamamoto Yasushi Yamamoto 1-10, Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd.Silicon Electronic Materials Research Laboratory (72) Inventor Noboru Shimamoto Usui-gun, Gunma 1-10 Hitomi, Matsuidacho, Shin-Etsu Chemical Co., Ltd.Silicon Electronic Materials Research Laboratory (72) Eiji Kuchiki 4-1-1 Tsukiji, Chuo-ku, Tokyo Tonen Chemical Co., Ltd. (72) Yuji Fujita 4-1-1 Tsukiji, Chuo-ku, Tokyo Inside Tonen Chemical Co., Ltd. (56) References JP-A-60-247556 (JP, A)

Claims (5)

(57) [Claims] (1) A random copolymer obtained by randomly copolymerizing a non-conjugated diene compound represented by the following general formula (1) with propylene: (However, R _{1 to} R ₄ are a hydrogen atom or an alkyl group, but R ₁ and R ₂ are not a methyl group and R ₃ is not a hydrogen atom at the same time. N represents an integer of 1 to 20.) (2) a graft copolymer obtained by graft-polymerizing a diene compound represented by the following general formula (2) onto polypropylene; (However, R _{1 to} R ₄ are a hydrogen atom or an alkyl group,
m shows the integer of 0-20. (3) As a first step, a monomer compound having both an unsaturated bond and a functional group is block-copolymerized with propylene, or graft-polymerized to polypropylene by a radical method, and then reacted with a functional group as a second step. A polypropylene resin having an aliphatic unsaturated bond selected from a modified polypropylene having an unsaturated bond introduced into the polypropylene or a composition containing the resin, Or an addition molded silicone rubber containing the compound of [II], wherein the addition molded silicone rubber is integrated with the silicone resin. [I] A compound having at least one hydrogen atom directly bonded to a silicon atom in one molecule and containing one or more groups selected from an alkoxysilyl group, a glycidyl group and an acid anhydride group. [II] One molecule has at least one hydrogen atom directly bonded to a silicon atom, and is a divalent-(CR ¹ R ² ) _n -bond (where n is an integer of 2 to 30, R ¹ and R ² is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms). 2. A polypropylene-based resin obtained by integrating a polypropylene-based resin having an aliphatic unsaturated bond or a composition containing said resin with an addition-type silicone rubber containing a compound of the following [II]: And molded silicone rubber. [II] One molecule has at least one hydrogen atom directly bonded to a silicon atom, and is a divalent-(CR ¹ R ² ) _n -bond (where n is an integer of 2 to 30, R ¹ and R ² is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms). 3. A random copolymer obtained by randomly copolymerizing a non-conjugated diene compound represented by the following general formula (1) with propylene: (However, R _{1 to} R ₄ are a hydrogen atom or an alkyl group, but R ₁ and R ₂ are not a methyl group and R ₃ is not a hydrogen atom at the same time. N represents an integer of 1 to 20.) (2) a graft copolymer obtained by graft-polymerizing a diene compound represented by the following general formula (2) to polypropylene; (However, R _{1 to} R ₄ are a hydrogen atom or an alkyl group,
m shows the integer of 0-20. (3) As a first step, a monomer compound having both an unsaturated bond and a functional group is block-copolymerized with propylene, or graft-polymerized to polypropylene by a radical method, and then reacted with a functional group as a second step. Reacting with a compound having a functional group and having an unsaturated bond to form a polypropylene-based resin having an aliphatic unsaturated bond selected from modified polypropylene having an unsaturated bond introduced into polypropylene or a molded article of a composition containing the resin. (A) an alkenyl group-containing organopolysiloxane, (b) an organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to silicon atoms in one molecule, (c) an addition reaction catalyst, (d) Or a silicone rubber composition containing the compound of [II]. Propylene-based resin or the manufacturing method of the integrally molded body of the polypropylene resin and the silicone rubber which is characterized by curing the silicone rubber composition at a temperature below the softening temperature the temperature of the composition comprising the resin. [I] A compound having at least one hydrogen atom directly bonded to a silicon atom in one molecule and containing one or more groups selected from an alkoxysilyl group, a glycidyl group and an acid anhydride group. [II] a divalent-(CR ¹ R ² ) _n -bond having at least one hydrogen atom directly bonded to a silicon atom in one molecule, wherein n is an integer of 2 to 30, R ¹ and R ² is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms). 4. A molded article of a polypropylene resin having an aliphatic unsaturated bond or a composition containing the resin, comprising: (a) an alkenyl group-containing organopolysiloxane; and (b) one molecule of a hydrogen atom directly bonded to a silicon atom. (C) a catalyst for addition reaction, (d) a silicone rubber composition containing a compound of the following [II], and then containing the above-mentioned polypropylene resin or the above-mentioned resin. A method for producing an integrally molded article of a polypropylene resin and silicone rubber, wherein the silicone rubber composition is cured at a temperature lower than the softening temperature of the composition. [II] a divalent-(CR ¹ R ² ) _n -bond having at least one hydrogen atom directly bonded to a silicon atom in one molecule, wherein n is an integer of 2 to 30, R ¹ and R ² is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms). 5. The method according to claim 3, wherein the molding of the molded article of the polypropylene-based resin or the composition containing the resin and the contact of the silicone rubber composition with the molded article are performed by injection molding.