JP2013094997A - Method of manufacturing adhered article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an adhered article by insert molding which enables strong joining of an insert part with a thermoplastic polymer composition even when the temperature of the insert part is relatively low, i.e., 30-150°C.SOLUTION: The method of manufacturing an adhered article is based on insert molding which includes filling a mold retaining an insert part with a thermoplastic polymer composition and molding. It uses a thermoplastic polymer composition containing 1-100 pts.mass of (B) polyvinyl acetal resin, 5-100 pts.mass of (C) an olefinic copolymer containing polar groups, and 0.1-300 pts.mass of (D) a softening agent to 100 pts.mass of a thermoplastic elastomer (A) consisting of a block copolymer composed of polymer blocks containing thermo-aromatic vinyl compound units and polymer blocks containing conjugated diene compound units or a hydrogenated product of the block copolymer. At insert molding, the temperature of the insert part 4 is adjusted to 30-150°C.

Description

  The present invention relates to a method for manufacturing an adhesive body. More specifically, the present invention relates to a method of manufacturing an adhesive body in which an insert part such as ceramics or metal and a thermoplastic elastomer are firmly joined by insert molding.

  Ceramics, metals, and synthetic resins with excellent durability, heat resistance, and mechanical strength are widely used in various applications such as home appliances, electronic parts, mechanical parts, and automobile parts. Depending on the application, component configuration and usage, etc., these members can be bonded or combined with highly flexible elastomer members for the purpose of fixing to other structural members or for purposes such as shock absorption, damage prevention or sealing. There are cases where it is used. Insert molding is an effective means for bonding or compounding different materials in this way.

  As the elastomer member, a styrenic thermoplastic elastomer having excellent flexibility and mechanical properties, and further excellent molding processability may be used. Here, the styrenic thermoplastic elastomer refers to a block copolymer having a polymer block composed of an aromatic vinyl compound unit and a polymer block composed of a conjugated diene compound unit or a hydrogenated product thereof. However, since the styrene-based thermoplastic elastomer is a material having low polarity, it has a problem that the adhesive strength to ceramics, metal and the like is not sufficient and it is difficult to bond by insert molding as it is. On the other hand, in order to bond ceramics or metal to a styrene-based thermoplastic elastomer, a method of applying an adhesive or preliminarily treating the surface of ceramics, metal, or synthetic resin is disclosed (Patent Document 1). To 6). However, the methods disclosed in Patent Documents 1 to 6 have problems that not only the process is complicated, but also the productivity is lowered and the manufacturing cost is increased.

  For such problems, a thermoplastic polymer composition containing a styrene-based thermoplastic elastomer and polyvinyl acetal having excellent adhesion to ceramics, metals and synthetic resins has been disclosed (see Patent Document 7). . Since this thermoplastic polymer composition can be bonded to ceramics, metal, and synthetic resin only by heat treatment without applying an adhesive or primer treatment, insert molding can be applied.

JP 2006-291019 A JP 2006-206715 A JP-A 63-25005 Japanese Patent Laid-Open No. 9-156035 JP 2009-227844 A JP 2010-1364 A International Publication No. 2009/081877 Pamphlet

However, in order to obtain an adhesive body with an insert part by insert molding using the thermoplastic polymer composition disclosed in Patent Document 7, the insert part is heated to a temperature equal to or higher than the flow starting point of the thermoplastic polymer composition ( There is a problem that the thermoplastic polymer composition is greatly contracted and deformed in the cooling process, and the desired shape cannot be obtained. In addition, since enormous energy is required for heating and cooling, and the molding cycle time becomes long, it is actually difficult to obtain an adhesive body with ceramics and metal by insert molding.
Thus, an object of the present invention is to produce an adhesive by insert molding that can firmly join the insert part and the thermoplastic polymer composition even when the temperature of the insert part is relatively low at 30 to 150 ° C. It is to provide a method.

According to the present invention, the above problem is
[1] A method for producing an adhesive by insert molding in which a mold holding an insert part is filled with a thermoplastic polymer composition and molded.
A block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit or a thermoplastic elastomer (A) which is a hydrogenated product thereof (hereinafter referred to as a thermoplastic elastomer (A ))) To 100 parts by mass, polyvinyl acetal resin (B) 1 to 100 parts by mass, polar group-containing olefin copolymer (C) 5 to 100 parts by mass and softener (D) 0.1 to 100 parts by mass. A method for producing an adhesive, comprising using a thermoplastic polymer composition containing 300 parts by mass, and setting the temperature of an insert part during insert molding to 30 to 150 ° C;
[2] In the thermoplastic polymer composition, the content of the component (B) is 10 to 70 parts by mass and the content of the component (C) is 10 to 70 with respect to 100 parts by mass of the thermoplastic elastomer (A). The method for producing an adhesive body according to the above [1], wherein the content of the component (D) is 1 to 200 parts by mass;
[3] The above-mentioned [1], wherein the polyvinyl acetal resin (B) is obtained by acetalizing polyvinyl alcohol having an average polymerization degree of 100 to 4,000, and the acetalization degree is 55 to 88 mol%. [2] method for producing an adhesive body;
[4] The method for producing an adhesive body according to the above [1] to [3], wherein the polyvinyl acetal resin (B) is polyvinyl butyral;
[5] The above olefin copolymer, wherein the polar group-containing olefin copolymer (C) is obtained by polymerizing an olefin copolymerizable monomer and a polar group-containing copolymerizable monomer. 1] to [4] method for producing an adhesive body;
[6] The above, wherein the polar group-containing olefin copolymer (C) has a melt flow rate (MFR) of 0.1 to 100 g / 10 min under the conditions of 190 ° C. and a load of 2.16 kg (21.18 N). [5] method for producing an adhesive body;
[7] The method for producing an adhesive body according to the above [1] to [6], wherein the Vicat softening point of the polar group-containing olefin copolymer (C) is 40 to 100 ° C.
[8] Adhesion of [5] to [7] above, wherein the proportion of the structural unit derived from the polar group-containing copolymerizable monomer of the polar group-containing olefin copolymer (C) is 1 to 50% by mass. Body manufacturing method;
[9] The method for producing an adhesive body according to the above [5] to [8], wherein the polar group-containing olefin copolymer (C) is an olefin- (meth) acrylic acid ester copolymer;
[10] The method for producing an adhesive body according to the above [1] to [9], wherein at least one selected from the group consisting of metals and ceramics is used as the insert part;
[11] The method for producing an adhesive body according to any one of [1] to [10], wherein the temperature of the insert part is controlled by a heating element;
[12] The method for producing an adhesive body according to [11] above, wherein the heating element is an electric heater, an electromagnetic induction heater, or a heat medium; and [13] The above [1] to [12], wherein a hot runner is used during insert molding. The method for producing an adhesive body of the present invention is provided.

According to the present invention, it is possible to obtain an adhesive body in which an insert part and a thermoplastic polymer composition are firmly joined even when the temperature of the insert part at the time of insert molding is a relatively low temperature of 30 to 150 ° C. it can. The adhesive body obtained by the present invention is free from deformation, sink marks, cracks and the like, and is excellent in appearance.
According to the present invention, since it is not necessary to heat the insert part to a high temperature (about 180 to 300 ° C.) above the flow starting point of the thermoplastic polymer composition, the shrinkage of the thermoplastic polymer composition during the cooling process.・ Deformation is greatly reduced. In addition, since the energy required for heating and cooling is reduced and the molding cycle time is shortened, an adhesive body between the insert part and the thermoplastic polymer composition can be produced under industrially advantageous conditions.

It is a front view of the movable side metal mold | die for insert molding employ | adopted by the Example and the comparative example. It is a cross-sectional view of the movable side mold for insert molding, which is employed in Examples and Comparative Examples. It is a longitudinal cross-sectional view of the movable mold for insert molding which was employ | adopted by the Example and the comparative example. It is a front view of the fixed side metal mold | die for insert molding employ | adopted by the Example and the comparative example. It is a cross-sectional view of a fixed mold for insert molding employed in Examples and Comparative Examples. It is a longitudinal cross-sectional view of the fixed side metal mold | die for insert molding employ | adopted by the Example and the comparative example.

[Method of manufacturing an adhesive body by insert molding]
The present invention relates to a method for producing an adhesive by insert molding in which a thermoplastic polymer composition is filled in a mold holding an insert part, and the polymer block containing an aromatic vinyl compound unit and a conjugated diene 1 to 100 parts by mass of a polyvinyl acetal resin (B) with respect to 100 parts by mass of a thermoplastic elastomer (A) which is a block copolymer having a polymer block containing a compound unit or a hydrogenated product thereof, containing a polar group A thermoplastic polymer composition containing 5 to 100 parts by mass of an olefin copolymer (C) and 0.1 to 300 parts by mass of a softening agent (D) is used, and the temperature of the insert part at the time of insert molding is 30. It is the manufacturing method of an adhesive body made into -150 degreeC.
First, the thermoplastic polymer composition will be described below, and then the insert molding conditions and the like will be described.

{Thermoplastic polymer composition}
The thermoplastic polymer composition used in the present invention comprises 1 to 100 parts by mass of a polyvinyl acetal resin (B) and 100 parts by mass of a polar group-containing olefin copolymer (C) with respect to 100 parts by mass of the thermoplastic elastomer (A). -100 mass parts and a softener (D) 0.1-300 mass parts are contained.

(Thermoplastic elastomer (A))
The thermoplastic elastomer (A) imparts flexibility, good mechanical properties, molding processability, and the like to the thermoplastic polymer composition, and serves as a matrix in the composition.
<Polymer block containing aromatic vinyl compound unit>
Examples of the aromatic vinyl compound constituting the polymer block containing the aromatic vinyl compound unit include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, Examples include 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. The polymer block containing the aromatic vinyl compound unit may be composed of a structural unit derived from only one of these aromatic vinyl compounds, or may be composed of a structural unit derived from two or more types. . Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferable.

Here, in the present invention, the “polymer block containing an aromatic vinyl compound unit” is preferably a polymer block containing 80% by mass or more of an aromatic vinyl compound unit, more preferably an aromatic vinyl compound unit 90. A polymer block containing at least mass%, more preferably a polymer block containing 95% by mass or more of aromatic vinyl compound units (both are values in terms of raw material charge amount). The polymer block containing the aromatic vinyl compound unit may have only the aromatic vinyl compound unit. However, as long as the effect of the present invention is not impaired, other copolymerizable units may be used together with the aromatic vinyl compound unit. It may have a monomer unit.
Examples of other copolymerizable monomers include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether. In the case of having other copolymerizable monomer units, the proportion thereof is preferably 20% by mass or less, more preferably 10%, based on the total amount of the aromatic vinyl compound unit and other copolymerizable monomer units. It is not more than mass%, more preferably not more than 5 mass%.

<Polymer block containing conjugated diene compound unit>
Examples of the conjugated diene compound constituting the polymer block containing the conjugated diene compound unit include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Can be mentioned. Among these, butadiene and isoprene are preferable.
The polymer block containing a conjugated diene compound unit may be composed of a structural unit derived from only one of these conjugated diene compounds, or may be composed of a structural unit derived from two or more types. In particular, it is preferably composed of a structural unit derived from butadiene or isoprene or a structural unit derived from butadiene and isoprene.

The bonding form of the conjugated diene constituting the polymer block containing the conjugated diene compound unit is not particularly limited. For example, in the case of butadiene, 1,2-bond and 1,4-bond can be formed, and in the case of isoprene, 1,2-bond, 3,4-bond and 1,4-bond can be formed. Among them, when the polymer block composed of conjugated diene compound units is composed of butadiene, when composed of isoprene, or when composed of both butadiene and isoprene, the amount of 1,4-bond in the polymer block composed of conjugated diene compound units Is preferably 1 to 99 mol%, more preferably 60 to 98 mol%, more preferably 80 to 98 mol%, and still more preferably 90 to 98 mol%.
The amount of 1,4-bond can be calculated by ¹ H-NMR measurement.

In the present invention, the “polymer block containing a conjugated diene compound unit” is preferably a polymer block containing 80 mol% or more of a conjugated diene compound unit, and more preferably a polymer block containing 90 mol% or more of a conjugated diene compound unit. A polymer block, more preferably a polymer block containing 95 mol% or more of conjugated diene compound units (both are values in terms of raw material charge amount). The polymer block containing the conjugated diene compound unit may have only the conjugated diene compound unit. However, as long as the effect of the present invention is not impaired, other copolymerizable monomer units together with the conjugated diene compound unit. You may have.
Examples of other copolymerizable monomers include styrene, α-methylstyrene, 4-methylstyrene, and the like. In the case of having other copolymerizable monomer units, the proportion thereof is preferably 20% by mass or less, more preferably 10% by mass with respect to the total amount of the conjugated diene compound unit and the other copolymerizable monomer units. % Or less, more preferably 5% by mass or less.

In the thermoplastic elastomer (A), the bonding form of the polymer block containing the aromatic vinyl compound unit and the polymer block containing the conjugated diene compound is linear, branched, radial, or two or more thereof Any of the bonding forms in which is combined may be used, but it is preferably linear.
For example, when a polymer block containing an aromatic vinyl compound unit is represented by a and a polymer block containing a conjugated diene compound is represented by b, a diblock copolymer represented by ab, ab- a triblock copolymer represented by a or b-a-b, a tetrablock copolymer represented by ab-a-b, a-b-a-b-a or b-a-b- A pentablock copolymer represented by a-b can be cited as a linear bond form. Among these, a triblock copolymer is preferable, and a triblock copolymer represented by aba is more preferable.

  In the thermoplastic elastomer (A), from the viewpoint of improving heat resistance and weather resistance, a part or all of the polymer block containing a conjugated diene compound unit may be hydrogenated (hereinafter abbreviated as “hydrogenated”). It is preferable that The hydrogenation rate of the polymer block containing the conjugated diene compound unit at that time is preferably 80% or more, more preferably 90% or more. Here, in this specification, the hydrogenation rate is a value obtained by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.

The content of the polymer block containing the aromatic vinyl compound unit in the thermoplastic elastomer (A) is preferably 5 to 75 mass with respect to the entire thermoplastic elastomer (A) from the viewpoint of flexibility and mechanical properties. %, More preferably, it is 10-60 mass%, More preferably, it is 15-40 mass%.
The weight average molecular weight of the thermoplastic elastomer (A) is preferably 30,000 to 300,000, more preferably 50,000 to 200,000, from the viewpoints of its mechanical properties and molding processability. Here, the weight average molecular weight is a standard polystyrene equivalent weight average molecular weight determined by gel permeation chromatography (GPC) measurement.
A thermoplastic elastomer (A) may be used individually by 1 type, and may be used in combination of 2 or more type. In particular, combining two types of medium molecular weight products with a weight average molecular weight of 50,000 to 150,000 and high molecular weight products with a weight average molecular weight of 150,000 to 300,000 will provide a better balance of mechanical properties, molding processability and adhesiveness. Since it becomes easy to take, it is preferable. For the same reason, when two kinds are combined, the medium molecular weight product / the high molecular weight product (mass ratio) is preferably 10/90 to 90/10, more preferably 20/80 to 75/25, and even more preferably. Is 20/80 to 55/45.

(Method for producing thermoplastic elastomer (A))
The thermoplastic elastomer (A) can be produced, for example, by an anionic polymerization method. In particular,
(I) a method of sequentially polymerizing the aromatic vinyl compound, the conjugated diene compound, and then the aromatic vinyl compound using an alkyl lithium compound as an initiator;
(Ii) a method in which an alkyl lithium compound is used as an initiator, the aromatic vinyl compound and the conjugated diene compound are sequentially polymerized, and then a coupling agent is added to perform coupling;
(Iii) A method of sequentially polymerizing the conjugated diene compound and then the aromatic vinyl compound using a dilithium compound as an initiator.

  Examples of the alkyl lithium compound in (i) and (ii) include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, pentyl lithium and the like. Examples of the coupling agent in (ii) include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene and the like. Examples of the dilithium compound in (iii) include naphthalene dilithium and dilithiohexylbenzene.

The amounts of initiators and coupling agents such as these alkyllithium compounds and dilithium compounds are determined by the weight average molecular weight of the target thermoplastic elastomer (A), and the aromatic vinyl compound used in the anionic polymerization method and In general, 0.01 to 0.2 parts by mass of an initiator such as an alkyllithium compound and a dilithium compound are usually used for 100 parts by mass of the conjugated diene compound. In (ii), the coupling agent is usually used in an amount of 0.001 to 0.8 parts by mass with respect to 100 parts by mass in total of the aromatic vinyl compound and the conjugated diene compound used in the anionic polymerization method.
The anionic polymerization is preferably performed in the presence of a solvent. The solvent is not particularly limited as long as it is inert to the initiator and does not adversely affect the polymerization. For example, saturated aliphatic hydrocarbons such as hexane, heptane, octane, decane; toluene, benzene, xylene, etc. And aromatic hydrocarbons. Moreover, it is preferable to superpose | polymerize normally at 0-80 degreeC for 0.5 to 50 hours also by any above-mentioned method.

During the anionic polymerization, the amount of 1,2-bond and 3,4-bond of the thermoplastic elastomer (A) can be increased by adding an organic Lewis base.
Examples of the organic Lewis base include esters such as ethyl acetate; amines such as triethylamine, N, N, N ′, N′-tetramethylethylenediamine (TMEDA), and N-methylmorpholine; nitrogen-containing heterocyclic groups such as pyridine. Aromatic compounds; Amides such as dimethylacetamide; Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF) and dioxane; Glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; Sulphoxides such as dimethyl sulfoxide; Ketones such as acetone and methyl ethyl ketone Can be mentioned.

After the polymerization by the above method, the block copolymer contained in the reaction solution is solidified by pouring it into a poor solvent of the block copolymer such as methanol, or the reaction solution is poured into hot water together with steam. After removing the solvent by azeotropic distillation (steam stripping), the unhydrogenated thermoplastic elastomer (A) can be isolated by drying.
Furthermore, the hydrogenated thermoplastic elastomer (A) can be produced by subjecting the unhydrogenated thermoplastic elastomer (A) obtained above to a hydrogenation reaction. In the hydrogenation reaction, the unhydrogenated thermoplastic elastomer (A) obtained above is dissolved in a solvent inert to the reaction and the hydrogenation catalyst, or the unhydrogenated thermoplastic elastomer (A) is dissolved. Can be used as is without isolation from the reaction solution, and reacted with hydrogen in the presence of a hydrogenation catalyst.
Examples of the hydrogenation catalyst include Raney nickel; heterogeneous catalyst in which a metal such as Pt, Pd, Ru, Rh, Ni is supported on a carrier such as carbon, alumina, diatomaceous earth; transition metal compound, alkylaluminum compound, alkyllithium compound Ziegler catalysts composed of a combination with the above; metallocene catalysts and the like.
The hydrogenation reaction can usually be carried out under conditions of a hydrogen pressure of 0.1 to 20 MPa, a reaction temperature of 20 to 250 ° C., and a reaction time of 0.1 to 100 hours. In this method, the hydrogenation reaction liquid is poured into a poor solvent such as methanol to solidify, or the hydrogenation reaction liquid is poured into hot water together with steam and the solvent is removed azeotropically (steam stripping). By drying, the hydrogenated thermoplastic elastomer (A) can be isolated.

Further, as the thermoplastic elastomer (A), a thermoplastic elastomer having a thermoplastic polyurethane block may be used in order to improve properties such as adhesion of the thermoplastic polymer composition used in the present invention. The thermoplastic elastomer having a thermoplastic polyurethane block has, for example, a thermoplastic polyurethane elastomer, a polymer block containing an aromatic vinyl compound unit containing a hydroxyl group at a terminal, and a polymer block containing a conjugated diene compound unit. It is obtained by kneading and reacting with a thermoplastic elastomer under melting conditions, and extracting and recovering from the resulting reaction product by a known method. As the thermoplastic polyurethane, polyester-based polyurethane is preferable, and polyester-based polyurethane having an aliphatic polyester as a soft segment is more preferable. As the thermoplastic polyurethane, “Kuramylon (registered trademark)” series manufactured by Kuraray Co., Ltd. can be used.
The mixing ratio of both is, by mass ratio, thermoplastic elastomer (A) before melt-kneading / thermoplastic polyurethane = 20 / 80-80 / 20 is preferable, 30 / 70-70 / 30 is more preferable, and 40 / 60- 60/40 is more preferable.

(Polyvinyl acetal resin (B))
The polyvinyl acetal resin (B) imparts adhesiveness to the thermoplastic polymer composition used in the present invention, and is usually dispersed in islands in the composition. By virtue of the presence of the polyvinyl acetal resin (B), the surface of the adherend such as ceramic, metal or synthetic resin can be satisfactorily bonded without being subjected to primer treatment.
The polyvinyl acetal resin (B) is usually a resin having a repeating unit represented by the following formula (I).

In the above formula (I), n represents the number of types of aldehyde used in the acetalization reaction. _{R 1, R 2, ···,} R n represents an alkyl residue or a hydrogen atom of aldehyde used for the acetalization _{reaction, k (1), k (} 2), ···, k (n) is , Each represents a ratio (molar ratio) of structural units represented by []. L represents the proportion (molar ratio) of vinyl alcohol units, and m represents the proportion (molar ratio) of vinyl acetate units.
However, k ₍₁₎ + k ₍₂₎ + ... + k _(n) + l + m = 1, and k ₍₁₎ , k ₍₂₎ , ..., k _(n) , l and m are any May be zero.
Each repeating unit is not particularly limited by the above-described arrangement order, and may be arranged at random, may be arranged in a block shape, or may be arranged in a taper shape.

(Production method of polyvinyl acetal resin (B))
The polyvinyl acetal resin (B) can be obtained, for example, by reacting polyvinyl alcohol and an aldehyde.
The average degree of polymerization of the polyvinyl alcohol used for the production of the polyvinyl acetal resin (B) is usually preferably 100 to 4,000, more preferably 100 to 3,000, still more preferably 100 to 2,000, particularly preferably. Is 250-2,000. If the average degree of polymerization of polyvinyl alcohol is 100 or more, the production of the polyvinyl acetal resin (B) becomes easy and the handleability is good. When the average degree of polymerization of polyvinyl alcohol is 4,000 or less, the melt viscosity at the time of melt kneading does not become too high, and the production of the thermoplastic polymer composition used in the present invention is easy.
Here, the average degree of polymerization of polyvinyl alcohol is measured according to JIS K 6726. Specifically, it is a value determined from the intrinsic viscosity measured in 30 ° C. water after re-saponifying and purifying polyvinyl alcohol.

  The production method of polyvinyl alcohol is not particularly limited, and for example, a product produced by saponifying polyvinyl acetate or the like with alkali, acid, aqueous ammonia, or the like can be used. Moreover, you may use a commercial item. Examples of commercially available products include “Kuraray Poval” series manufactured by Kuraray Co., Ltd. Polyvinyl alcohol may be completely saponified or partially saponified. The saponification degree is preferably 80 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more.

  Moreover, as said polyvinyl alcohol, the copolymer of vinyl alcohol, such as an ethylene-vinyl alcohol copolymer and a partly saponified ethylene-vinyl alcohol copolymer, and the monomer copolymerizable with vinyl alcohol can be used. Furthermore, modified polyvinyl alcohol in which carboxylic acid or the like is partially introduced can be used. These polyvinyl alcohols may be used individually by 1 type, and may be used in combination of 2 or more type.

  The aldehyde used for production of the polyvinyl acetal resin (B) is not particularly limited. For example, formaldehyde (including paraformaldehyde), acetaldehyde (including paraacetaldehyde), propionaldehyde, n-butyraldehyde, isobutyraldehyde, pentanal, hexanal, heptanal, n-octanal, 2-ethylhexylaldehyde, cyclohexanecarbaldehyde, furfural, Examples include glyoxal, glutaraldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde and the like. These aldehydes may be used individually by 1 type, and may be used in combination of 2 or more type. Of these aldehydes, butyraldehyde is preferred and n-butyraldehyde is more preferred from the viewpoint of ease of production.

The polyvinyl acetal resin (B) obtained by acetalization using butyraldehyde is particularly referred to as polyvinyl butyral (PVB).
In the present invention, the proportion of butyral units (see the following formula) among the acetal units present in the polyvinyl acetal resin (B) is preferably 0.8 or more, more preferably 0.9 or more, and still more preferably 0.8. 95 or more, particularly preferably substantially 1.
That is, in the structural formula of the polyvinyl acetal resin (B) represented by the formula (I), when only R ₁ is C ₃ H ₇ , 0.8 ≦ k ₍₁₎ / (k ₍₁₎ + k _{(2 )} +... + K _(n) ) is preferred.

The degree of acetalization of the polyvinyl acetal resin (B) used in the present invention is preferably 55 to 88 mol%. The polyvinyl acetal resin (B) having an acetalization degree of 55 mol% or more is low in production cost, easily available, and has good melt processability. On the other hand, the polyvinyl acetal resin (B) having an acetalization degree of 88 mol% or less is very easy to produce, and is economical because it does not require a long time for the acetalization reaction.
The degree of acetalization of the polyvinyl acetal resin (B) is more preferably 60 to 88 mol%, further preferably 70 to 88 mol%, and particularly preferably 75 to 85 mol%. The lower the degree of acetalization of the polyvinyl acetal resin (B), the larger the proportion of hydroxyl groups that the polyvinyl acetal resin (B) has, which is advantageous in adhesion to ceramics, metals and synthetic resins. As a result, the affinity and compatibility with the thermoplastic elastomer (A) are improved, the mechanical properties of the thermoplastic polymer composition are excellent, and the adhesive strength with ceramics, metal and synthetic resin is increased.

The degree of acetalization (mol%) of the polyvinyl acetal resin (B) is defined by the following formula.
Degree of acetalization (mol%) = {k ₍₁₎ + k ₍₂₎ + ... + k _(n) } × 2 / {{k ₍₁₎ + k ₍₂₎ + ... + k _(n) } × 2 + l + m } × 100
(In the above formula, n, k ₍₁₎ , k ₍₂₎ ,..., K _(n) , l and m are as defined above.)

The degree of acetalization of the polyvinyl acetal resin (B) can be determined according to the method described in JIS K 6728 (1977). That is, the mass proportion of vinyl alcohol units (l ₀ ) and the mass proportion of vinyl acetate units (m ₀ ) are determined by titration, and the mass proportion of vinyl acetal units (k ₀ ) is determined by k ₀ = 1−l ₀ -m ₀ . Ask. From this, the molar ratio l [l = (l ₀ /44.1)/(l ₀ /44.1+m ₀ /86.1+2k ₀ / Mw (acetal)] of vinyl alcohol units and the molar ratio m [m = m of vinyl acetate units _{(m 0 /86.1)/(l 0 /44.1+m 0 /86.1+2k} 0 / Mw ( acetal) is calculated and the molar ratio of the vinyl acetal units by formula of k = 1-l-m ( k = k ₍₁₎ + k ₍₂₎ +... + k _(n) ), where Mw (acetal) is the molecular weight per vinyl acetal unit, and for example, when polyvinyl butyral, Mw ( Acetal) = Mw (butyral) = 142.2 and {k ₍₁₎ + k ₍₂₎ +... + K _(n) } × 2 / {{k ₍₁₎ + k ₍₂₎ +. by _{· + k (n)} ×} 2 + l + m} calculation formula × 100, acetal It can be obtained degree (mol%).
The degree of acetalization of the polyvinyl acetal resin (B) is determined by dissolving the polyvinyl acetal resin (B) in an appropriate deuterated solvent such as deuterated dimethyl sulfoxide, and measuring ¹ H-NMR or ¹³ C-NMR. May be calculated.

  The polyvinyl acetal resin (B) preferably contains 12 to 45 mol% (0.12 ≦ l ≦ 0.45) of vinyl alcohol units, and preferably 0 to 5 mol% (0 ≦ m) of vinyl acetate units. ≦ 0.05), more preferably 0 to 3 mol% (0 ≦ m ≦ 0.03).

The reaction (acetalization reaction) between polyvinyl alcohol and aldehyde can be performed by a known method. For example, an aqueous solution method in which an aqueous solution of polyvinyl alcohol and an aldehyde are acetalized in the presence of an acid catalyst to precipitate particles of the polyvinyl acetal resin (B); polyvinyl alcohol is dispersed in an organic solvent, and an acid catalyst Solvent method for precipitating polyvinyl acetal resin (B) by acetalization reaction with aldehyde in the presence, and mixing the obtained reaction mixture with water, which is a poor solvent for polyvinyl acetal resin (B). Etc.
The acid catalyst is not particularly limited, and examples thereof include organic acids such as acetic acid and p-toluenesulfonic acid; inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid; gas which shows acidity when an aqueous solution such as carbon dioxide is used; cation exchange Examples thereof include solid acid catalysts such as resins and metal oxides.

The slurry produced in the aqueous medium method or the solvent method is usually acidic by an acid catalyst. As a method for removing the acid catalyst, the slurry is repeatedly washed with water, and the pH is preferably adjusted to 5-9, more preferably 6-9, and even more preferably 6-8; a neutralizing agent is added to the slurry. A method of adjusting the pH to preferably 5 to 9, more preferably 6 to 9, and even more preferably 6 to 8; a method of adding alkylene oxides to the slurry, and the like.
Examples of the compound used for adjusting the pH include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal acetates such as sodium acetate; alkali metal such as sodium carbonate and potassium carbonate; Examples thereof include carbonates; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; ammonia and aqueous ammonia solutions. Examples of the alkylene oxides include ethylene oxide, propylene oxide; glycidyl ethers such as ethylene glycol diglycidyl ether.

Next, salts generated by neutralization, aldehyde reaction residues, and the like are removed.
The removal method is not particularly limited, and methods such as repeated dehydration and water washing are usually used. The water-containing polyvinyl acetal resin (B) from which residues and the like have been removed is dried as necessary and processed into powder, granules, or pellets as necessary.
As the polyvinyl acetal resin (B) used in the present invention, a resin obtained by reducing the aldehyde reaction residue, moisture, etc. by degassing under reduced pressure when processed into a powder, granule or pellet. preferable.

  The thermoplastic polymer composition used in the present invention contains 1 to 100 parts by mass of the polyvinyl acetal resin (B) with respect to 100 parts by mass of the thermoplastic elastomer (A). When the polyvinyl acetal resin (B) is less than 1 part by mass, it is difficult to obtain sufficient adhesion with ceramics, metal and synthetic resin. On the other hand, when the amount of the polyvinyl acetal resin (B) is more than 100 parts by mass, sufficient adhesiveness can be obtained, but the thermoplastic polymer composition becomes hard and flexibility and mechanical properties are hardly exhibited. The content of the polyvinyl acetal resin (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, particularly preferably 100 parts by mass of the thermoplastic elastomer (A). It is 25 parts by mass or more, more preferably 70 parts by mass or less, further preferably 50 parts by mass or less, and particularly preferably 45 parts by mass or less. Accordingly, the content of the polyvinyl acetal resin (B) is preferably 1 to 70 parts by mass, more preferably 5 to 70 parts by mass, and more preferably 10 to 70 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). It is 10-50 mass parts, More preferably, it is 20-50 mass parts, More preferably, it is 25-45 mass parts.

(Polar group-containing olefin copolymer (C))
The polar group-containing olefin copolymer (C) not only imparts good moldability to the thermoplastic polymer composition used in the present invention, but the thermoplastic polymer composition is at 150 ° C. or less. It also makes it possible to adhere well to ceramics, metals or synthetic resins.
Examples of the polar group of the polar group-containing olefin copolymer (C) include an ester group, a hydroxyl group, an amide group, and a halogen atom such as a chlorine atom.
As the polar group-containing olefin copolymer (C), an olefin copolymer comprising an olefin copolymerizable monomer and a polar group-containing copolymerizable monomer is preferable. Examples of the olefin copolymerizable monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclohexene and the like. These may be used individually by 1 type and may combine 2 or more types. Among these, ethylene and propylene are preferable, and ethylene is more preferable. Examples of the polar group-containing copolymerizable monomer include (meth) acrylic acid ester, (meth) acrylic acid, vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, and acrylamide. These may be used individually by 1 type and may combine 2 or more types. Of these, (meth) acrylic acid esters are preferred.

  Specific examples of (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, and acrylic acid. Acrylic acid alkyl esters such as isohexyl, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid Examples thereof include alkyl methacrylates such as isobutyl, n-hexyl methacrylate, isohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate and 2-ethylhexyl methacrylate. These (meth) acrylic acid esters may be used alone or in combination of two or more. Among them, alkyl acrylate is preferable, methyl acrylate and ethyl acrylate are more preferable, and methyl acrylate is more preferable from the viewpoint of obtaining high adhesiveness even at 150 ° C. or lower.

The polymerization form of the polar group-containing olefin copolymer (C) is not particularly limited, and a random copolymer, a block copolymer, or the like can be used. Among these, a random copolymer is preferable.
The polar group contained in the polar group-containing olefin copolymer (C) may be post-treated after polymerization. For example, neutralization with a metal ion of (meth) acrylic acid may be performed to obtain an ionomer, or hydrolysis of vinyl acetate may be performed.

  The melt flow rate (MFR) of the polar group-containing olefin copolymer (C) under the conditions of 190 ° C. and a load of 2.16 kg (21.18 N) is preferably 0.1 to 100 g / 10 minutes, more preferably 0.1 to 70 g / 10 min, more preferably 0.1 to 50 g / 10 min, more preferably 1 to 30 g / 10 min, still more preferably 1 to 20 g / 10 min, particularly preferably 1 to 10 g / min. is there. If the MFR of the polar group-containing olefin copolymer (C) is 0.1 g / 10 min or more under the above conditions, sufficient adhesive strength can be obtained even at 150 ° C. or less. On the other hand, when the MFR is 100 g / 10 min or less, it is easy to obtain and mechanical characteristics are easily developed.

  The Vicat softening point of the polar group-containing olefin copolymer (C) is preferably 40 to 100 ° C, more preferably 45 to 95 ° C, more preferably 45 to 75 ° C, still more preferably 45 to 65 ° C, particularly preferably. Is 45-55 ° C. When the Vicat softening point of the polar group-containing olefin copolymer (C) is 40 ° C. or higher, the mechanical properties of the thermoplastic polymer composition will be good. If the Vicat softening point is 100 ° C. or lower, the adhesive strength is increased even at 150 ° C. or lower. The Vicat softening point is a value measured by the A50 method in accordance with JIS K 7206.

The ratio of the polar group-containing structural unit of the polar group-containing olefin copolymer (C) to the total structural unit of the polar group-containing olefin copolymer (C) is preferably 1 to 50% by mass, More preferably, it is 1-40 mass%, Most preferably, it is 10-30 mass%. When the proportion of the polar group-containing structural unit is within this range, the affinity and compatibility with the thermoplastic elastomer (A) and the compatibility with the polyvinyl acetal resin (B) are good, and the heat The mechanical properties of the plastic polymer composition are improved, the adhesiveness to ceramics, metal and synthetic resin is increased, and the adhesive strength is increased even at 150 ° C. or lower.
As the proportion of the polar group-containing structural unit decreases, the mechanical properties of the thermoplastic polymer composition tend to decrease, and as the proportion of the polar group-containing structural unit increases, the thermoplastic elastomer (A ) Tend to be less compatible and compatible.

The thermoplastic polymer composition used in the present invention contains 5 to 100 parts by mass of the polar group-containing olefin copolymer (C) with respect to 100 parts by mass of the thermoplastic elastomer (A). If the polar group-containing olefin copolymer (C) is less than 5 parts by mass, it is difficult to bond the ceramic, metal or synthetic resin at 150 ° C. or lower. On the other hand, when the polar group-containing olefin copolymer (C) is more than 100 parts by mass, sufficient adhesiveness can be obtained, but the thermoplastic polymer composition becomes hard and flexibility and mechanical properties are hardly exhibited. . The content of the polar group-containing olefin copolymer (C) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 35 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). It is above, More preferably, it is 70 mass parts or less, More preferably, it is 60 mass parts or less.
From these, the content of the polar group-containing olefin copolymer (C) is preferably 5 to 70 parts by weight, more preferably 10 to 70 parts by weight, and more preferably 100 parts by weight of the thermoplastic elastomer (A). Preferably it is 20-70 mass parts, Most preferably, it is 35-60 mass parts.

(Softener (D))
As the softener (D), for example, softeners generally used for rubber and plastics can be used.
For example, paraffinic, naphthenic and aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil, mineral oil, ethylene and α-olefin oligomers, paraffin wax, liquid paraffin, polybutene, low molecular weight polybutadiene And low molecular weight polyisoprene. Among these, process oil is preferable, and paraffinic process oil is more preferable.
Also, known softeners generally used in combination with polyvinyl acetal resins, for example, organic acid ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters; organic phosphate esters, organic phosphorus Phosphoric plasticizers such as acid esters can also be used.
Examples of the monobasic organic acid ester include triethylene glycol-dicaproic acid ester, triethylene glycol-di-2-ethylbutyric acid ester, triethylene glycol-di-n-octylic acid ester, triethylene glycol-di-2. -Glycols such as triethylene glycol, tetraethylene glycol, and tripropylene glycol typified by ethyl hexyl ester, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid And glycol esters obtained by reaction with monobasic organic acids such as pelargonic acid (n-nonyl acid) and decyl acid.
Examples of the polybasic acid organic esters include linear or linear polybasic organic acids such as adipic acid, sebacic acid, azelaic acid and the like represented by sebacic acid dibutyl ester, azelaic acid dioctyl ester, adipic acid dibutyl carbitol ester and the like. Examples include esters of branched alcohols.
Examples of the organic phosphate ester include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.
A softener (D) may be used individually by 1 type, and may be used in combination of 2 or more type.

The thermoplastic polymer composition used in the present invention contains 0.1 to 300 parts by mass of the softening agent (D) with respect to 100 parts by mass of the thermoplastic elastomer (A). When the softening agent (D) is less than 0.1 parts by mass, the flexibility and moldability of the thermoplastic polymer composition are lowered. Preferably it is 1 mass part or more, More preferably, it is 10 mass parts or more, More preferably, it is 50 mass parts or more. On the other hand, when the softening agent (D) is more than 300 parts by mass, the mechanical properties, adhesion to ceramics, metal and synthetic resin are lowered. More preferably, it is 200 mass parts or less. More preferably, it is 150 mass parts or less.
Accordingly, the content of the softening agent (D) is preferably 1 to 200 parts by weight, more preferably 10 to 200 parts by weight, and still more preferably 50 to 200 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer (A). Part, particularly preferably 50 to 150 parts by weight.

(Other optional ingredients)
The thermoplastic polymer composition used in the present invention is not limited to the effects of the present invention, and other thermoplastics such as an olefin polymer, a styrene polymer, a polyphenylene ether resin, and a polyethylene glycol as necessary. A polymer may be contained. Among these, when the thermoplastic polymer composition used in the present invention contains an olefin polymer, the molding processability and mechanical properties are further improved. Examples of such an olefin polymer include polyethylene, polypropylene, polybutene, one or two types such as block copolymers and random copolymers of propylene and other α-olefins such as ethylene and 1-butene. The above can be used.
When other thermoplastic polymer is contained, the content thereof is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, more preferably 20 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). Hereinafter, it is more preferably 10 parts by mass or less.

The thermoplastic polymer composition used for this invention can contain an inorganic filler as needed. The inorganic filler is useful for improving the physical properties such as heat resistance and weather resistance of the thermoplastic polymer composition, adjusting the hardness, and improving the economical efficiency as an extender. The inorganic filler is not particularly limited. For example, calcium carbonate, talc, magnesium hydroxide, aluminum hydroxide, mica, clay, natural silicic acid, synthetic silicic acid, titanium oxide, carbon black, barium sulfate, glass balloon, Glass fiber etc. are mentioned. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.
When the inorganic filler is contained, the content thereof is preferably within a range in which the flexibility of the thermoplastic polymer composition is not impaired, and is generally preferably 100 with respect to 100 parts by mass of the thermoplastic elastomer (A). It is not more than part by mass, more preferably not more than 70 parts by mass, further preferably not more than 30 parts by mass, particularly preferably not more than 10 parts by mass.

In addition, the thermoplastic polymer composition used in the present invention can further contain a tackifying resin as long as the effects of the present invention are not impaired. Examples of tackifying resins include rosin resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, coumarone / indene resins, Examples thereof include phenolic resins and xylene resins.
When the tackifying resin is contained, the content thereof is preferably in a range that does not impair the mechanical properties of the thermoplastic polymer composition, and is generally preferably 100 with respect to 100 parts by mass of the thermoplastic elastomer (A). It is not more than part by mass, more preferably not more than 70 parts by mass, further preferably not more than 30 parts by mass, particularly preferably not more than 10 parts by mass.

The thermoplastic polymer composition used in the present invention may further include an antioxidant, a lubricant, a light stabilizer, a processing aid, a colorant such as a pigment or a dye, and the like, as long as the effects of the invention are not impaired. A flame retardant, an antistatic agent, a matting agent, silicone oil, an antiblocking agent, an ultraviolet absorber, a release agent, a foaming agent, an antibacterial agent, an antifungal agent, and a fragrance may be contained.
Examples of the antioxidant include hindered phenol-based, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Among these, hindered phenol antioxidants are preferable. When the antioxidant is contained, the content thereof is preferably in a range not colored when the resulting thermoplastic polymer composition is melt-kneaded, and preferably with respect to 100 parts by mass of the thermoplastic elastomer (A). Is 0.1 to 5 parts by mass.

  There is no particular limitation on the method for preparing the thermoplastic polymer composition used in the present invention, and any method can be used as long as the above components can be uniformly mixed. Usually, a melt-kneading method is used. . Melt-kneading can be performed using, for example, a melt-kneading apparatus such as a single-screw extruder, a twin-screw extruder, a kneader, a batch mixer, a roller, a Banbury mixer, and the melt-kneading is usually preferably performed at 170 to 270 ° C. Thus, the thermoplastic polymer composition used in the present invention can be obtained.

  The thermoplastic polymer composition thus obtained has a hardness according to the JIS-A method of JIS K 6253 (hereinafter sometimes referred to as “A hardness”), preferably 93 or less, more preferably 30 to 85, Preferably it is 40-75, Most preferably, it is 40-60. If the A hardness is too high, it is difficult to obtain good flexibility, elasticity and mechanical properties, and heat having excellent adhesion to synthetic resins, especially resins containing inorganic fillers (such as glass fibers), ceramics and metals. There exists a tendency for the suitable use as a plastic polymer composition to become difficult.

{Insert parts}
In the present invention, as described above, an adhesive body is manufactured by insert molding in which a mold holding an insert part is filled with the thermoplastic polymer composition and molded. Here, "insert molding" refers to inserting the insert part and the thermoplastic polymer by inserting an insert part such as a metal material into a mold having a predetermined shape and then filling the thermoplastic polymer composition. This is a method for obtaining a molded product integrated with a composition. There is no restriction | limiting in particular in the method of hold | maintaining an insert component in a metal mold | die, A well-known method can be employ | adopted, For example, the method of fixing using a pin etc. and the method of fixing with a vacuum line are mentioned. In the present invention, the “adhesive” refers to an insert part and a thermoplastic polymer composition that are bonded and integrated.
As the insert part used in the present invention, at least one selected from the group consisting of glass, ceramics, metal, and metal plating is preferably used, and the insert part is ceramic, metal, or metal plated. Is more preferable.
Ceramics means a non-metallic inorganic material, and examples thereof include metal oxides, metal carbides, and metal nitrides. Specifically, cements, alumina, zirconia, zinc oxide based ceramics, barium titanate, lead zirconate titanate, silicon carbide, silicon nitride, ferrites and the like can be mentioned.
Examples of the metal include iron, copper, aluminum, magnesium, nickel, chromium, zinc, and alloys containing these as components. Examples of the metal plating include copper plating, nickel plating, chrome plating, tin plating, zinc plating, platinum plating, gold plating, and silver plating.
In addition, light metals such as synthetic resin, aluminum, and magnesium alloys are used for housing materials such as electronic / electrical equipment, OA equipment, home appliances, and automobile members. Naturally, such housing materials should be used as insert parts. You can also.

{Mold}
Although there is no restriction | limiting in particular in the metal mold | die used at the time of insert molding, For example, it is preferable to use a metal mold | die as shown in FIGS.
1 to 3 are a front view, a transverse sectional view, and a longitudinal sectional view of the movable mold, respectively. FIGS. 4 to 6 are a front view, a transverse sectional view, and a longitudinal sectional view of the fixed mold, respectively.
Although two cavities CAV1 and CAV2 are shown in FIG. 1, the cavities are dug to different depths, and CAV1 and CAV2 can be selected by switching the flow paths. Moreover, the insert part (4) installed in the cavity can be fixed by the vacuum line (2). 2 and 3 show a state in which the insert part (4) and the thermoplastic polymer composition (5) are installed in the cavity. FIG. 4 shows a mold temperature adjusting water channel (6), and the thick arrows in FIGS. 1, 5, and 6 indicate the route through which the thermoplastic polymer composition is filled from the cylinder.

(Insert molding conditions)
In the present invention, the temperature of the insert part during insert molding greatly reduces the shrinkage and deformation of the thermoplastic polymer composition during the cooling process, reduces the energy required for heating and cooling, and shortens the molding cycle time. From the viewpoint of making it, it is 30 to 150 ° C. In the present invention, by using the specific thermoplastic polymer composition, sufficient adhesive strength is obtained between the insert part and the thermoplastic polymer composition even if the temperature of the insert part is within the temperature range. It is done.
From the above viewpoint, the temperature of the insert part is preferably 50 to 150 ° C, more preferably 80 to 150 ° C, still more preferably 100 to 150 ° C, and particularly preferably 120 to 140 ° C. When the temperature is lower than 30 ° C., it is necessary to separately provide a cooling facility, and there is a possibility that sufficient adhesive strength between the insert part and the thermoplastic polymer composition cannot be obtained. On the other hand, if the temperature exceeds 150 ° C., the thermoplastic resin composition shrinks and deforms during the cooling process, making it difficult to obtain the desired shape, increasing the energy required for heating and cooling, and increasing the molding cycle time. Increase.

There is no particular limitation on the method of setting the temperature of the insert part at the time of insert molding in the above range, and there are a method of performing through a temperature control mechanism of a mold and a method of providing a mechanism for selectively controlling the temperature of the insert part. It is done. When the temperature is lower than 150 ° C., a method performed through a temperature control mechanism of the mold is simple. On the other hand, when the temperature is set to 50 ° C. or higher, a method of providing a mechanism for selectively controlling the temperature of the insert part is preferable from the viewpoint of easy temperature control.
“Mold temperature control mechanism” is a function of the mold that adjusts the temperature of the mold itself. “Mechanism for selectively controlling the temperature of the insert part” means that it is close to the insert part. This is a temperature control function dedicated to insert parts.
By selectively controlling the temperature of the insert part, the temperature of the insert part can be easily raised, and the adhesive can be easily released from the mold. For selective control of the temperature of the insert part, a heating element such as an electric heater, an electromagnetic induction heater, a heat medium, or a hot plate can be used.
When an electric heater or an electromagnetic induction heater is used, it can be used by being embedded in a mold, or a heating plate embedded with a heater can be attached to the mold surface. In the case of using a heat medium, there is a method in which a heat medium flow path is provided in a mold, a heat medium having a predetermined temperature is supplied from the outside, and discharged to the outside. Although there is no restriction | limiting in particular as a heat medium, Fluids, such as oil, water, water vapor | steam, air, nitrogen, combustion gas, are mentioned.
In addition, when a metal is used for the insert part, it may be directly energized and heated, or may be induction heated by an induction coil.
Moreover, there is no restriction | limiting in particular in the time to hold | maintain the temperature of insert components in the said range, From a viewpoint of production efficiency, Preferably it is less than 3 minutes, More preferably, it is less than 2 minutes, From an adhesive viewpoint, Preferably It is 5 seconds or more, more preferably 15 seconds or more, and further preferably 30 seconds or more. In addition, sufficient adhesive force is obtained even if it transfers to the cooling operation mentioned later immediately, without providing holding time substantially.
In order to adjust the temperature of the insert part more efficiently, it is also effective to provide a heat insulating structure between the periphery of the insert part and the mold.

As a procedure for setting the temperature of the insert part within the above range,
(1) A method of keeping the insert part at a predetermined temperature before filling the mold holding the insert part with the thermoplastic polymer composition [hereinafter sometimes referred to as a preheating method. ],
(2) A method in which the temperature is not adjusted at the stage of filling the thermoplastic polymer composition, and the temperature is raised to a predetermined temperature in the mold after filling [hereinafter sometimes referred to as a post-heating method. ],
(3) A method of raising the temperature to some extent at the stage of filling the thermoplastic polymer composition, and further raising the temperature to a predetermined temperature in the mold after filling,
Etc. Among these, from the viewpoint of adhesiveness control, the methods (1) and (2) are preferable. From the viewpoint of ease of temperature control of the insert part, the method (1) is more preferable, and from the viewpoint of the appearance of the bonded body Therefore, the method (2) is more preferable.
In the case of (1) above, the temperature control of the insert part may be stopped immediately after the operation of filling the thermoplastic polymer composition into the mold is started, or during the filling of the thermoplastic polymer composition. The temperature adjustment of the insert part may be continued.

  After the insert part is heated to the predetermined temperature to obtain an adhesive body, the adhesive body obtained is taken out (released) from the mold, and the adhesive body is cooled as necessary. It is preferable that the surface temperature of the bonded body is 30 to 50 ° C. before the bonded body is removed from the mold. There is no restriction | limiting in particular in the cooling method, For example, the method (here also including natural cooling) performed via the temperature control mechanism of a metal mold | die is mentioned. It is also possible to shorten the cooling time by arranging the flow path of the cooling medium in the vicinity of the adhesive body. In particular, when the temperature of the insert part is selectively controlled using a heat medium, the heat medium can be switched to a cooling medium and cooled by using the flow path of the heat medium.

  In the present invention, a hot runner can be used at the time of insert molding as a means by which the removal of the solidified resin in the mold channel (for example, sprue, runner and gate) can be omitted and the adhesive can be easily released. Can be used. As the heating method of the hot runner, either an internal heating method or an external heating method can be used. Examples of the hot runner gate seal system include a thermal balance system and a valve gate system. Examples of the seal by thermal balance include a hot tip, a sprue gate, and a hot edge.

  In the present invention, an injection molding method is used, but an injection compression molding method can also be employed to reduce sink marks, voids and molding distortion of the thermoplastic polymer composition. The injection compression molding method also has an effect of increasing the adhesive force to the insert part.

  The adhesive strength of the thermoplastic polymer composition in the adhesive body obtained as described above is usually preferably 20 N / 25 mm or more, more preferably 25 N / 25 mm or more, which is hardly peeled by human hands, and more preferably 30 N / 25 mm or more is more preferable, and it is usually in a range of 25 to 50 N / 25 mm. If it is less than 20 N / 25 mm, it can be easily peeled off although it has resistance, and it cannot be said that it is sufficiently bonded from the viewpoint of practicality. Here, the adhesive strength is a value measured according to JIS K 6854-2 by the method described in Examples.

There is no restriction | limiting in particular in the shape of an adhesive body to which the manufacturing method of this invention is applied, a structure, a use, etc. INDUSTRIAL APPLICABILITY The present invention is useful for manufacturing a bonding portion between glass and an aluminum sash or a metal opening in a window of an automobile or a building, and manufacturing a connecting portion between glass and a metal frame in a solar cell module or the like. Also, shock absorbers for housings such as large displays, notebook computers, mobile phones, PHS, PDAs (personal information terminals such as electronic notebooks), electronic dictionaries, video cameras, digital still cameras, portable radio cassette players, and inverters It is useful for a method of molding a covering material having a non-slip prevention function, a waterproof material, a design material, and the like.
Furthermore, it is useful for manufacturing various information terminal devices such as notebook computers, mobile phones, video cameras, secondary battery separators used in hybrid vehicles, fuel cell vehicles, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by this Example.
The thermoplastic elastomer (A), polyvinyl acetal resin (B), polar group-containing olefin copolymer (C) and softener (D) used in the following examples and comparative examples are as follows. Using.

[(Styrene-based) thermoplastic elastomer (A1)]
A pressure-resistant container purged with nitrogen and dried is charged with 80 L of cyclohexane as a solvent and 0.17 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator, heated to 50 ° C., and then added with 3.9 L of styrene. The mixture was polymerized for 3 hours, followed by addition of a mixed solution of 12.1 L of isoprene and 10.9 L of butadiene for 4 hours of polymerization, and further 3.9 L of styrene was added for 3 hours of polymerization. The obtained reaction solution was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene-poly (isoprene / butadiene) -polystyrene.
Subsequently, 20 kg of a triblock copolymer composed of polystyrene-poly (isoprene / butadiene) -polystyrene is dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) is added to the copolymer as a hydrogenation catalyst. The reaction was carried out for 10 hours under the conditions of a hydrogen pressure of 2 MPa and 150 ° C. After allowing to cool and release the pressure, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to give a hydrogenated triblock copolymer (hereinafter referred to as polystyrene) -poly (isoprene / butadiene) -polystyrene A thermoplastic elastomer (A1)). The resulting thermoplastic elastomer (A1) has a weight average molecular weight of 170,000, a styrene content of 32% by mass, a hydrogenation rate of 97%, a molecular weight distribution of 1.04, and a 1,4-bond content of 95 mol%. there were.

[(Styrene) thermoplastic elastomer (A2)]
A pressure-resistant container purged with nitrogen and dried is charged with 80 L of cyclohexane as a solvent and 0.34 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator, heated to 50 ° C., and then added with 4.0 L of styrene. The mixture was polymerized for 3 hours, followed by addition of a mixed solution of 14.2 L of isoprene and 11.6 L of butadiene for 4 hours of polymerization, and 4.0 L of styrene was further added for 3 hours of polymerization. The obtained reaction solution was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene-poly (isoprene / butadiene) -polystyrene.
Subsequently, 20 kg of a triblock copolymer composed of polystyrene-poly (isoprene / butadiene) -polystyrene is dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) is added to the copolymer as a hydrogenation catalyst. The reaction was carried out for 10 hours under the conditions of a hydrogen pressure of 2 MPa and 150 ° C. After allowing to cool and release the pressure, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to give a hydrogenated triblock copolymer (hereinafter referred to as polystyrene) -poly (isoprene / butadiene) -polystyrene A thermoplastic elastomer (A2)). The resulting thermoplastic elastomer (A2) has a weight average molecular weight of 100,000, a styrene content of 30% by mass, a hydrogenation rate of 97%, a molecular weight distribution of 1.02, and a 1,4-bond content of 95 mol%. there were.

[Polyvinyl acetal resin (B1)]
N-Butyraldehyde and an acid catalyst (hydrochloric acid) were added to an aqueous solution in which a polyvinyl alcohol resin having an average polymerization degree of 500 and a saponification degree of 99 mol% was dissolved, and the mixture was stirred to acetalize to precipitate a resin. Wash until pH = 6 according to known methods, then suspend in alkaline aqueous medium and work up with stirring, wash until pH = 7, volatiles to 0.3% By drying to the end, a polyvinyl acetal resin (B1) having an acetalization degree of 80 mol% was obtained.
[Polyvinyl acetal resin (B2)]
N-Butyraldehyde and an acid catalyst (hydrochloric acid) were added to an aqueous solution in which a polyvinyl alcohol resin having an average polymerization degree of 1000 and a saponification degree of 99 mol% was dissolved, and the mixture was stirred to acetalize to precipitate a resin. Wash until pH = 6 according to known methods, then suspend in alkaline aqueous medium and work up with stirring, wash until pH = 7, volatiles to 0.3% By drying to the end, a polyvinyl acetal resin (B2) having an acetalization degree of 80 mol% was obtained.

[Polar group-containing olefin copolymer (C1)]
Ethylene-methyl acrylate copolymer “Elvalloy (registered trademark) AC 1820AC” (methyl acrylate content: 20% by mass, MFR [190 ° C., load 2.16 kg (21.18 N)]: 8 g / 10 min, Vicat Softening point: 54 ° C, Mitsui DuPont Polychemical Co., Ltd.)
[Polar group-containing olefin copolymer (C2)]
Ethylene-methyl acrylate copolymer “Elvalloy (registered trademark) AC 1609AC” (methyl acrylate content: 9% by mass, MFR [190 ° C., load 2.16 kg (21.18 N)]: 6 g / 10 min, Vicat (Softening point: 70 ° C, Mitsui DuPont Polychemical Co., Ltd.)
[Polar group-containing olefin copolymer (C3)]
Ethylene-methyl acrylate copolymer “Elvalloy (registered trademark) AC 1125AC” (methyl acrylate content: 25 mass%, MFR [190 ° C., load 2.16 kg (21.18 N)]: 0.4 g / 10 min Vicat softening point: 48 ° C., Mitsui DuPont Polychemical Co., Ltd.)
[Polar group-containing olefin copolymer (C4)]
Ethylene-ethyl acrylate copolymer “ethylene-ethyl acrylate copolymer NUC-6170” (ethyl acrylate content: 18% by mass, MFR [190 ° C., load 2.16 kg (21.18 N)]: 6 g / 10 min., Vicat softening point: 58 ° C, manufactured by Nihon Unicar Co., Ltd.)
[Olefin copolymer (C'5)]
Low density polyethylene “Novatech LD LC607K” (trade name, MFR [190 ° C., load 2.16 kg (21.18 N)]: 8 g / 10 min, Vicat softening point: 89 ° C., manufactured by Nippon Polyethylene Co., Ltd.)

[Softener (D1)]
Paraffinic process oil “Diana Process PW-90” (trade name, manufactured by Idemitsu Kosan Co., Ltd.)

<Manufacture of pellets and sheets of thermoplastic polymer composition>
Each component described above is mixed at a mass ratio described in the table, melt-kneaded using a twin screw extruder at 230 ° C. and screw rotation of 200 rpm, extruded into a strand, cut and thermoplastic polymer. A pellet of the composition was obtained.
In order to measure each physical property of the produced thermoplastic polymer composition, the pellet is compression molded using a compression molding machine at 230 ° C. under a load of 100 kgf / cm ² (9.8 N / mm ² ) for 3 minutes. A thermoplastic polymer composition sheet having a thickness of 1 mm was obtained. Measurement and evaluation of each physical property of the obtained thermoplastic polymer composition sheet were performed as follows. The results are shown in Table 1.

(Measurement of melt flow rate (MFR))
MFR was measured for the thermoplastic polymer composition pellets under the conditions of 230 ° C. and a load of 2.16 kg (21.18 N) by a method according to JIS K 7210, and used as an index for molding processability evaluation. The larger the MFR value, the better the moldability.
(Measurement of hardness)
A thermoplastic polymer composition sheet was stacked to prepare a test piece having a thickness of 6 mm, and the type A hardness was measured with a type A durometer according to JIS K 6253.
(Tensile breaking strength (Tb) and tensile breaking elongation (Eb))
A dumbbell-shaped test piece (dumbbell-shaped No. 5) was produced from the thermoplastic polymer composition sheet by a method according to JIS K 6251, and the tensile strength at break and the tensile elongation at break were measured at a tensile speed of 500 mm / min. .

The insert parts used in the following examples or comparative examples are as follows.
[Insert part (a): Aluminum plate (A5052P)]
[Insert part (b): Steel plate (SPCC)]
[Insert part (c): electrogalvanized steel sheet (SECC)]
[Insert part (d): SUS304]
[Insert part (e): Copper plate (C1100P)]
The surfaces of both surfaces of each insert part having a length of 100 mm, a width of 35 mm, and a thickness of 1 mm were washed using a surfactant aqueous solution and distilled water in this order, and dried at 65 ° C.

Moreover, the measurement of the adhesive force of the thermoplastic polymer composition of the adhesive body obtained in the following Examples or Comparative Examples and the evaluation of the appearance were performed as follows.
(Measurement of adhesive strength)
A sheet made of polyethylene terephthalate was adhered to the thermoplastic polymer composition side of the obtained adhesive with an adhesive, and in accordance with JIS K 6854-2, an insert part was formed under conditions of a peeling angle of 180 ° and a tensile speed of 50 mm / min. The adhesive strength of the thermoplastic polymer composition was measured.
(Appearance evaluation)
The appearance of the bonded body was visually evaluated according to the following evaluation criteria. When none of deformation, sink, and crack was observed in the thermoplastic polymer composition portion, “◯” was indicated. When at least one of deformation, sink, and crack was observed, “X” was assigned.

<Examples 1-8 and Comparative Examples 1-7>
1 to 6 was used, and the insert part (a) was fixed in the mold by a vacuum line. The heater was energized and the insert part was adjusted to 140 ° C. by heat conduction. Under the conditions of a mold temperature of 30 ° C. and a cylinder temperature of 230 ° C., the thermoplastic polymer composition having the composition shown in Table 1 is filled into the CAV2, and immediately after the filling is started, the energization of the heater is stopped to The surface temperature of was cooled to 30 ° C. to obtain an adhesive. Table 1 shows the measurement results of the adhesive strength of the thermoplastic polymer composition of the obtained adhesive.

<Examples 9 to 13 and Comparative Example 8>
In Example 5, the same operation was performed except that the temperature of the insert part and the insert part was changed as shown in Table 2 to obtain an adhesive body.

<Example 14>
In Example 5, the same operation was performed except that the heater was turned off 15 seconds after the filling of the thermoplastic polymer composition was started, and an adhesive body was obtained.
Table 2 shows the measurement results of the adhesive strength of the thermoplastic polymer composition of the obtained adhesive.

From Table 1 and Table 2, even if the temperature of the insert part at the time of insert molding is 140 ° C. by using a thermoplastic polymer composition containing specific components (A) to (D) at a specific blending ratio, And it turns out that it is excellent in the adhesive force of the adhesive body obtained (Examples 1-8). In addition, by using the thermoplastic polymer composition, the temperature of the insert part at the time of insert molding is further lowered to 120 ° C. even for insert parts made of various materials such as aluminum, steel sheet, stainless steel, and galvanized steel sheet. Even if it becomes, it turns out that it is excellent in the adhesive force of the adhesive body obtained, and excellent in an external appearance (Examples 9-13). Moreover, the adhesive force could be further improved by maintaining the insert temperature for a certain period of time after filling with the thermoplastic polymer composition (Example 14).
On the other hand, in the case of a thermoplastic polymer composition that deviates from the provisions of the present invention, when the temperature of the insert part at the time of insert molding is 140 ° C., the adhesive strength of the obtained adhesive body is poor (Comparative Examples 1 to 7). ). In addition, even when the specific thermoplastic polymer composition defined in the present invention is used, if the temperature of the insert part is increased to 180 ° C., the thermoplastic polymer composition will sink, resulting in poor appearance. (Comparative Example 8).

INDUSTRIAL APPLICABILITY The present invention is useful for manufacturing a bonding portion between glass and an aluminum sash or a metal opening in a window of an automobile or a building, and manufacturing a connecting portion between glass and a metal frame in a solar cell module or the like. Also, shock absorbers for housings such as large displays, notebook computers, mobile phones, PHS, PDAs (personal information terminals such as electronic notebooks), electronic dictionaries, video cameras, digital still cameras, portable radio cassette players, and inverters It is useful for a method of molding a covering material having a non-slip prevention function, a waterproof material, a design material, and the like.
Furthermore, it is useful for manufacturing various information terminal devices such as notebook computers, mobile phones, video cameras, secondary battery separators used in hybrid vehicles, fuel cell vehicles, and the like.

DESCRIPTION OF SYMBOLS 1 Embedded heater 2 Vacuum line 3 Extrusion pin 4 Insert part 5 Thermoplastic polymer composition 6 Mold temperature control channel

Claims (13)

A method for producing an adhesive body by insert molding in which a mold holding an insert part is filled with a thermoplastic polymer composition and molded,
A block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit or a thermoplastic elastomer (A) which is a hydrogenated product thereof is used in a proportion of 100 parts by mass. A thermoplastic polymer composition containing 1 to 100 parts by mass of an acetal resin (B), 5 to 100 parts by mass of a polar group-containing olefin copolymer (C) and 0.1 to 300 parts by mass of a softening agent (D). And the temperature of the insert part at the time of insert molding is 30 to 150 ° C.   In the thermoplastic polymer composition, with respect to 100 parts by mass of the thermoplastic elastomer (A), the content of the component (B) is 10 to 70 parts by mass, the content of the component (C) is 10 to 70 parts by mass, The manufacturing method of the adhesive body of Claim 1 whose content of a component (D) is 1-200 mass parts.   The polyvinyl acetal resin (B) is obtained by acetalizing polyvinyl alcohol having an average polymerization degree of 100 to 4,000, and the acetalization degree is 55 to 88 mol% according to claim 1 or 2. Manufacturing method of adhesive body.   The manufacturing method of the adhesive body in any one of Claims 1-3 whose polyvinyl acetal resin (B) is polyvinyl butyral.   The polar group-containing olefin copolymer (C) is an olefin copolymer obtained by polymerizing an olefin copolymerizable monomer and a polar group-containing copolymerizable monomer. The manufacturing method of the adhesive body in any one of.   The melt flow rate (MFR) of the polar group-containing olefin copolymer (C) at 190 ° C. under a load of 2.16 kg (21.18 N) is 0.1 to 100 g / 10 min. The manufacturing method of the adhesive body of description.   The manufacturing method of the adhesive body in any one of Claims 1-6 whose Vicat softening point of a polar group containing olefin type copolymer (C) is 40-100 degreeC.   The adhesive body in any one of Claims 5-7 whose ratio of the structural unit derived from the polar group containing copolymerizable monomer of a polar group containing olefin type copolymer (C) is 1-50 mass%. Manufacturing method.   The manufacturing method of the adhesive body in any one of Claims 5-8 whose polar group containing olefin type copolymer (C) is an olefin- (meth) acrylic acid ester copolymer.   The manufacturing method of the adhesive body in any one of Claims 1-9 using at least 1 sort (s) selected from the group which consists of a metal and ceramics as said insert component.   The manufacturing method of the adhesive body in any one of Claims 1-10 which controls the temperature of insert components with a heat generating body.   The method for producing an adhesive body according to claim 11, wherein the heating element is an electric heater, an electromagnetic induction heater, or a heat medium.   The manufacturing method of the adhesive body of Claims 1-12 using a hot runner at the time of insert molding.