JP5785874B2 - Manufacturing method of adhesive body - Google Patents

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. Moreover, 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 or 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.
Polymer block containing aromatic vinyl compound unit, and polymer containing isoprene unit, butadiene unit or isoprene / butadiene unit in which 1,2-bond amount and 3,4-bond amount are 40 mol% or more in total Polyvinyl acetal resin (B) 1 to 100 with respect to 100 parts by mass of a block copolymer having a block or a thermoplastic elastomer (A) (hereinafter abbreviated as a thermoplastic elastomer (A)) which is a hydrogenated product thereof. Manufacture of an adhesive body using a thermoplastic polymer composition containing 5 parts by mass and 5 to 100 parts by mass of a polar group-containing polypropylene-based resin (C), and setting the temperature of the insert part during insert molding to 30 to 150 ° C Method;
[2] In the thermoplastic polymer composition, the content of the component (B) is 5 to 70 parts by mass and the content of the component (C) is 5 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], which is a mass part;
[3] The above [1] or [2], wherein the thermoplastic polymer composition further 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). Manufacturing method of
[4] The adhesive according to [1] to [3], wherein the thermoplastic polymer composition further contains 1 to 100 parts by mass of a tackifier resin (E) with respect to 100 parts by mass of the thermoplastic elastomer (A). Body manufacturing method;
[5] 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%. [4] method for producing an adhesive body;
[6] The method for producing an adhesive body according to the above [1] to [5], wherein the polar group-containing polypropylene resin (C) is a carboxylic acid-modified polypropylene resin;
[7] The method for producing an adhesive body according to the above [1] to [6], wherein at least one selected from the group consisting of metals and ceramics is used as the insert part;
[8] The method for producing an adhesive body according to the above [1] to [7], wherein the temperature of the insert part is controlled by a heating element;
[9] The method for producing an adhesive body according to [8], wherein the heating element is an electric heater, an electromagnetic induction heater, or a heat medium;
[10] The method for producing an adhesive body according to the above [1] to [9], wherein a hot runner is used during insert molding;
It is solved by providing.

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 body by insert molding in which a thermoplastic polymer composition is filled into a mold holding an insert part and molded, and a polymer block containing an aromatic vinyl compound unit, , 2-bond amount and 3,4-bond amount in combination with a block copolymer having an isoprene unit, a butadiene unit or a polymer block containing an isoprene / butadiene unit, or a hydrogenated product thereof A thermoplastic polymer composition containing 1 to 100 parts by mass of a polyvinyl acetal resin (B) and 5 to 100 parts by mass of a polar group-containing polypropylene resin (C) with respect to 100 parts by mass of a certain thermoplastic elastomer (A). It is the manufacturing method of an adhesive body which uses and the temperature of the insert components at the time of insert molding shall be 30-150 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 is 1 to 100 parts by mass of the polyvinyl acetal resin (B) and 5 to 100 parts by mass of the polar group-containing polypropylene resin (C) with respect to 100 parts by mass of the thermoplastic elastomer (A). Parts. The thermoplastic polymer composition may further contain a softening agent (D). In addition, the thermoplastic polymer composition may further contain a tackifier resin (E) in order to improve moldability.
Hereinafter, the components (A) to (E) will be described in order.

(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. In the present invention, as described above, in the polymer block containing an isoprene unit, a butadiene unit or an isoprene / butadiene unit, the amount of 1,2-bond and 3,4-bond are combined to be 40 mol% or more. In particular, the compatibility with the polar group-containing polypropylene resin (C) is enhanced, and it is assumed that the obtained thermoplastic polymer composition has high insert adhesiveness and high adhesiveness in a temperature environment of 60 ° C. or higher. Is done. In the present specification, the adhesiveness between the thermoplastic polymer composition and the insert part in a molded product obtained by insert molding may be referred to as “insert adhesiveness”.
<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. . Of 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% by mass or less, with respect to all constituent units of the polymer block containing the aromatic vinyl compound unit. More preferably, it is 5% by mass or less.

<Polymer block containing isoprene unit, butadiene unit or isoprene / butadiene unit>
Examples of the compound constituting the polymer block containing an isoprene unit, a butadiene unit, or an isoprene / butadiene unit include isoprene, butadiene, and 2,3-dimethyl-1,3-butadiene. Of these, isoprene and butadiene are preferred.

Regarding the bonding form of the compound constituting the polymer block containing the isoprene unit, the butadiene unit or the isoprene / butadiene unit (bonding form of isoprene, butadiene, and isoprene and butadiene), the temperature of the insert part is 30 to 150 ° C. From the viewpoints of adhesion and heat resistance, the amount of 1,2-bond and the amount of 3,4-bond need to be 40 mol% or more as described above. From the same viewpoint, the total amount of 1,2-bond and 3,4-bond is preferably 45 to 90 mol%, more preferably 50 to 85 mol%, and still more preferably 50 to 80 mol%. is there. A bond form other than 1,2-bond and 3,4-bond is 1,4-bond.
The 1,2-bond amount and 3,4-bond amount can be calculated by ¹ H-NMR measurement. Specifically, the integrated value of the peak existing at 4.2 to 5.0 ppm derived from 1,2-bond units and 3,4-bond units and 5.0-5 derived from 1,4-bond units. It can be calculated from the ratio with the integrated value of the peak existing at .45 ppm.

In the present invention, the “polymer block containing an isoprene unit, a butadiene unit or an isoprene / butadiene unit” is preferably 80% by mass or more, more preferably 90% by mass or more of an isoprene unit, a butadiene unit or an isoprene / butadiene unit. More preferably, it is a polymer block containing 95% by mass or more (both are values in terms of raw material charge amount). The polymer block may have only an isoprene unit, a butadiene unit or an isoprene / butadiene unit, but other than the isoprene unit, the butadiene unit or the isoprene / butadiene unit, as long as the effect of the present invention is not significantly impaired. It may have a copolymerizable monomer unit.
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 based on the total constituent units of the polymer block containing isoprene units, butadiene units or isoprene / butadiene units. Is 10% by mass or less, more preferably 5% by mass or less.

In the thermoplastic elastomer (A), the bonding form of the polymer block containing an aromatic vinyl compound unit and the polymer block containing an isoprene unit, a butadiene unit or an isoprene / butadiene unit is linear, branched or radial. Or any combination form in which two or more of these are combined, but is preferably a straight chain.
For example, when a polymer block containing an aromatic vinyl compound unit is represented by a and a polymer block containing an isoprene unit, a butadiene unit or an isoprene / butadiene unit is represented by b, a diblock copolymer represented by ab is represented. A polymer, a triblock copolymer represented by a-b-a or b-a-b, a tetra-block copolymer represented by a-b-a-b, a-b-a-b-a Or the pentablock copolymer represented by b-a-b-a-b is mentioned as a linear bond form. Especially, a triblock copolymer is preferable and it is more preferable that it is a triblock copolymer represented by aba.

  In the thermoplastic elastomer (A), from the viewpoint of improving heat resistance and weather resistance, a part or all of the polymer block containing an isoprene unit, a butadiene unit or an isoprene / butadiene unit is hydrogenated (hereinafter referred to as “hydrogenation”). (It may be abbreviated as “.”). At that time, the hydrogenation rate of the polymer block is preferably 80% or more, more preferably 90% or more. Here, in the present specification, the hydrogenation rate is a value obtained by measuring the iodine value of the thermoplastic elastomer (A) 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 5 to 60% by mass, still more preferably 10 to 40% by mass, and particularly preferably 10 to 25% by mass.
The weight average molecular weight of the thermoplastic elastomer (A) is preferably 30,000 to 500,000, more preferably 50,000 to 400,000, and still more preferably 100 from the viewpoints of mechanical properties and molding processability. , 000-200,000. 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.

As described above, the thermoplastic polymer composition used in the present invention contains the specific thermoplastic elastomer (A). In addition, “a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit having a 1,4-bond amount exceeding 60 mol% or hydrogenation thereof” In order not to significantly impair the effects of the present invention, the “polymer block containing an aromatic vinyl compound unit and the 1,4-bond amount of 60 mol%” may be included. The content of the block copolymer having a polymer block containing a conjugated diene compound unit exceeding or the hydrogenated product thereof is 120 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer (A). Preferably, more preferably 100 parts by weight or less, more preferably 40 parts by weight or less, more preferably 25 parts by weight or less, more preferably 10 parts by weight or less, Preferably not more than 5 parts by weight, particularly preferably substantially 0 mass parts. If the content is 120 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer (A), the mechanical properties such as tensile strength at break and tensile elongation at break are good, and further, it adheres to ceramics, metals or synthetic resins. The molded product thus formed is excellent in adhesiveness (heat resistance) under a temperature environment of 60 ° C. or higher and does not peel easily. This is presumed to be related to compatibility with the component (C) described later.
Each term in the above “” is explained in the same manner as described above except for the term “polymer block containing a conjugated diene compound unit having a 1,4-bond amount exceeding 60 mol%”. Is.

In the “polymer block containing a conjugated diene compound unit having a 1,4-bond amount exceeding 60 mol%”, examples of the conjugated diene compound from which the conjugated diene compound unit is derived include isoprene, butadiene, 2, 3 -Dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like.
The polymer block containing a conjugated diene compound unit in which the 1,4-bond amount exceeds 60 mol% may be composed of a structural unit derived from only one kind of the conjugated diene compound or derived from two or more kinds. It may consist of structural units that 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 1,4-bond amount can be calculated by the aforementioned ¹ H-NMR measurement.

(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, isoprene and / or the butadiene, 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, isoprene and / or the butadiene are sequentially polymerized, and then a coupling agent is added to perform coupling;
(Iii) A method of sequentially polymerizing isoprene and / or the butadiene 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 amount of the initiator or coupling agent such as these alkyllithium compounds and dilithium compounds is determined by the weight average molecular weight of the target thermoplastic elastomer (A), but the aromatic vinyl compound used in the anionic polymerization method, 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 isoprene and butadiene in total. In (ii), the coupling agent is generally 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, isoprene and butadiene 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, for example, by adding an organic Lewis base, the 1,2-bond amount and 3,4-bond amount of the thermoplastic elastomer (A) can be increased.
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. These organic Lewis bases may be used individually by 1 type, and may be used in combination of 2 or more type.
The organic Lewis base is used in an amount of, for example, lithium ions contained in the initiator from the viewpoint of setting the 1,2-bond amount and 3,4-bond amount of the thermoplastic elastomer (A) to 40 mol% or more. On the other hand, the stoichiometric ratio is preferably 0.01 to 1000 times, more preferably 0.1 to 100 times, and still more preferably 0.1 to 50 times. By adjusting the amount of the organic Lewis base used within this range, the 1,2-bond amount and 3,4-bond amount of the thermoplastic elastomer (A) can be arbitrarily controlled.

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 styrene thermoplastic elastomer (A) obtained above is dissolved in a solvent inert to the reaction and the hydrogenation catalyst, or the unhydrogenated styrene thermoplastic is obtained. The elastomer (A) can be used as it is without being isolated 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 styrenic thermoplastic elastomer (A) can be isolated.

(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 thermoplastic polymer 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.

  As the polyvinyl alcohol, a copolymer of vinyl alcohol and a monomer copolymerizable with vinyl alcohol, such as an ethylene-vinyl alcohol copolymer or a partially saponified ethylene-vinyl alcohol copolymer, 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 n-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; gases which show 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 or moisture by degassing under reduced pressure when processed into a powder, granule or pellet is 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 15 parts by mass or more, with respect to 100 parts by mass of the thermoplastic elastomer (A). Preferably it is 70 mass parts or less, More preferably, it is 50 mass parts or less, Most preferably, it is 45 mass parts 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 mass parts, More preferably, it is 10-50 mass parts, More preferably, it is 15-45 mass parts.

(Polar group-containing polypropylene resin (C))
The thermoplastic polymer composition used in the present invention contains a polar group-containing polypropylene resin (C) in addition to the thermoplastic elastomer (A) and the polyvinyl acetal resin (B). In addition to imparting better moldability to the composition, it becomes possible to adhere well to ceramics, metals or synthetic resins even at temperatures of 190 ° C. or lower, and to ceramics, metals or synthetic resins. Even when a molded article formed by bonding the thermoplastic polymer composition is exposed to a temperature environment of 60 ° C. or higher, high adhesiveness is maintained.
Examples of the polar group contained in the polar group-containing polypropylene resin (C) include (meth) acryloyloxy group; hydroxyl group; amide group; halogen atom such as chlorine atom; carboxyl group; The method for producing the polar group-containing polypropylene resin (C) is not particularly limited, but propylene (an α-olefin as necessary) and a polar group-containing copolymerizable monomer can be randomly co-polymerized by a known method. It can be obtained by polymerization, block copolymerization or graft copolymerization. In addition, it can also be obtained by subjecting a polypropylene resin to a reaction such as oxidation or chlorination by a known method.
The polar group-containing polypropylene resin (C) may be obtained by copolymerizing an α-olefin other than propylene with a polar group-containing copolymerizable monomer together with propylene. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclohexene and the like. The α-olefin can be copolymerized with a polar group-containing copolymer monomer by a known method, preferably random copolymer, block copolymer or graft copolymer, and more preferably random copolymer. . The proportion of units derived from α-olefins other than propylene to the total structural units of the polar group-containing polypropylene resin (C) is preferably 0 to 45 mol%, more preferably 0 to 35 mol%, and further Preferably it is 0-25 mol%.
Examples of the polar group-containing copolymerizable monomer include vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, acrylamide, unsaturated carboxylic acid, ester or anhydride thereof. Of these, unsaturated carboxylic acids or esters or anhydrides thereof are preferred. Examples of the unsaturated carboxylic acid or ester or anhydride thereof include (meth) acrylic acid, (meth) acrylic acid ester, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, highmic acid, and hymic anhydride. An acid etc. are mentioned. Of these, maleic acid and maleic anhydride are more preferable. These polar group-containing copolymerizable monomers may be used alone or in combination of two or more.
As the polar group-containing polypropylene resin (C), from the viewpoint of compatibility with the polyvinyl acetal resin (B), a polypropylene containing a carboxyl group as a polar group, that is, a carboxylic acid-modified polypropylene resin is preferable. More preferred are polypropylene resins and maleic anhydride-modified polypropylene resins.

  Specific examples of the (meth) acrylic acid ester exemplified as the polar group-containing copolymerizable monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-butyl acrylate. , Alkyl acrylates such as isobutyl acrylate, n-hexyl acrylate, isohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate Methacrylic acid such as isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate They include alkyl esters. 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 at a temperature of the insert part of 30 to 150 ° C.

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

The melt flow rate (MFR) of the polar group-containing olefin copolymer (C) under conditions of 230 ° C. and a load of 2.16 kg (21.18 N) is preferably 0.1 to 100 g / 10 min, 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 15 g / min. is there. If the MFR of the polar group-containing polypropylene resin (C) under the above conditions is 0.1 g / 10 min or more, sufficient adhesive strength at 190 ° C. or less can be obtained. 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 melting point of the polar group-containing polypropylene resin (C) is preferably 100 ° C. or higher, more preferably 110 to 170 ° C., and still more preferably 120 to 145 ° C., from the viewpoint of heat resistance.

The ratio of the polar group-containing structural unit of the polar group-containing polypropylene resin (C) to the total structural unit of the polar group-containing polypropylene resin (C) is preferably 0.01 to 10% by mass, more preferably 0. 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and particularly preferably 0.1 to 2% by 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, and the adhesive strength is increased even at the adhesiveness to ceramics, metal and synthetic resin and at a temperature of 30 to 150 ° C. of the insert part. You may use what diluted the polypropylene resin which has a polar group containing structural unit in high concentration with the polypropylene resin which does not have a polar group containing structural unit so that the ratio of a polar group containing structural unit may become the optimal.
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). When the polar group-containing olefin copolymer (C) is less than 5 parts by mass, it is difficult to bond ceramics, metal or synthetic resin at 190 ° 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 polypropylene resin (C) is more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more with respect to 100 parts by mass of the thermoplastic elastomer (A). More preferably, it is 70 mass parts or less, More preferably, it is 60 mass parts or less, Most preferably, it is 30 mass parts or less.
From these, the content of the polar group-containing polypropylene resin (C) is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, more preferably 100 parts by mass of the thermoplastic elastomer (A). It is 15-60 mass parts, More preferably, it is 15-30 mass parts, Most preferably, it is 20-30 mass parts.

(Softener (D))
Examples of the softening agent (D) that may further be contained in the thermoplastic polymer composition used in the present invention include softening agents generally used for rubber and plastics.
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. Of 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, etc. 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.

  When the softening agent (D) is contained in the thermoplastic polymer composition used in the present invention, the content is based on 100 parts by mass of the thermoplastic elastomer (A) from the viewpoints of flexibility, moldability and adhesiveness. The amount is preferably 0.1 to 300 parts by mass, more preferably 1 to 200 parts by mass, more preferably 10 to 200 parts by mass, still more preferably 50 to 200 parts by mass, and particularly preferably 50 to 150 parts by mass.

(Tackifying resin (E))
The thermoplastic polymer composition used in the present invention can further improve molding processability while maintaining adhesive properties by further containing a tackifier resin (E) as necessary.
Examples of such tackifier resins (E) include aliphatic unsaturated hydrocarbon resins, aliphatic saturated hydrocarbon resins, alicyclic unsaturated hydrocarbon resins, alicyclic saturated hydrocarbon resins, aromatic hydrocarbon resins, water Hydrogenated aromatic hydrocarbon resin, rosin ester resin, hydrogenated rosin ester resin, terpene phenol resin, hydrogenated terpene phenol resin, terpene resin, hydrogenated terpene resin, aromatic hydrocarbon modified terpene resin, coumarone / indene resin, phenol resin And xylene resin. Tackifying resin (E) may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, aliphatic saturated hydrocarbon resins, alicyclic saturated hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, and hydrogenated terpene resins are preferable.

The softening point of the tackifier resin (E) is preferably 50 to 200 ° C, more preferably 65 to 180 ° C, and further preferably 80 to 160 ° C. If the softening point is 50 ° C. or higher, the adhesive property with respect to the environmental temperature can be maintained. On the other hand, if the softening point is 200 ° C. or lower, the adhesive properties with respect to the heat treatment temperature can be maintained.
Here, the softening point is a value measured according to ASTM 28-67.

  When the thermoplastic polymer composition used in the present invention further contains a tackifier resin (E), the content is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). Preferably it is 5-70 mass parts, More preferably, it is 5-50 mass parts, Most preferably, it is 10-45 mass parts. If the content of the tackifying resin (E) is 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer (A), the thermoplastic polymer composition does not become hard, and flexibility and mechanical properties are easily exhibited. .

(Other optional ingredients)
The thermoplastic polymer composition used in the present invention is not limited to the effects of the present invention, and other thermoplastic heavy polymers such as olefin polymers, styrene polymers, polyphenylene ether resins, polyethylene glycol, etc. It may contain a coalescence. Among these, when an olefin polymer is contained, molding processability and mechanical properties are further improved. Examples of the olefin polymer include polyethylene, polypropylene, polybutene, block copolymers of propylene and other α-olefins such as ethylene and 1-butene, random copolymers, and the like. 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 5 parts by mass or less.

The thermoplastic polymer composition used in the present invention can contain an inorganic filler, if necessary. 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.

The thermoplastic polymer composition used in the present invention may further contain an antioxidant, a lubricant, a light stabilizer, a processing aid, a colorant such as a pigment or a dye, 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, a fragrance, and the like 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.

  The method for preparing the thermoplastic polymer composition used in the present invention is not particularly limited, and any method may be used as long as the above components can be mixed uniformly. Usually, a melt-kneading method is used. The melt-kneading can be performed using 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 is usually melt-kneaded preferably 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 90. More preferably, it is 40-85. If the A hardness is too high, flexibility, elasticity, and mechanical properties are hardly exhibited, and a thermoplastic resin having excellent adhesion to synthetic resins, particularly resins, ceramics, and metals containing inorganic fillers (glass fibers, etc.). There exists a tendency for the suitable use as a union composition to become difficult.

  The melt flow rate (MFR) of the thermoplastic polymer composition measured by a method according to JIS K 7210 at 230 ° C. and a load of 2.16 kg (21.18 N) is preferably 1 to It is in the range of 40 g / 10 min, more preferably 1-30 g / 10 min, and still more preferably 2-20 g / min. When the MFR is within this range, good moldability can be obtained, and the bonding step with a synthetic resin, particularly a synthetic resin containing an inorganic filler (such as glass fiber), ceramics, and metal becomes easy.

{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, metal-plated, and synthetic resin is preferably used. Ceramic, metal, metal-plated More preferably.
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.
Further, light metals such as synthetic resins, aluminum, and magnesium alloys are used for housing materials such as electronic / electrical equipment, OA equipment, home appliances, and automobile members, and such housing materials can also be used as insert parts. .

{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. Excellent insert adhesion.
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 115 to 145 ° 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 set to 50 ° C. or lower, a method performed through a mold temperature control mechanism 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, but from a viewpoint of insert adhesiveness, 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 them, the method (1) or (2) is preferable from the viewpoint of insert adhesiveness control, the method (1) is more preferable from the viewpoint of ease of temperature control of the insert part, and from the viewpoint of the appearance of the bonded body. 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 (insert adhesiveness) of the thermoplastic polymer composition in the adhesive body obtained as described above is usually preferably 20 N / 25 mm or more, and is preferably 25 N / 25 mm or more, which is hardly peeled by human power. More preferably, it is more preferably 30 N / 25 mm or more, and is usually in the range of 20 to 85 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, a waterproof material, a design material or the like having an anti-slip function.
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 etc. demonstrate 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 polypropylene resin (C), softener (D) and tackifier resin (E) used in the following examples and comparative examples are as follows. The following were used.

[Thermoplastic elastomer (A1)]
A pressure-resistant vessel purged with nitrogen and dried was charged with 64 L of cyclohexane as a solvent, 0.20 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator, and 0.3 L of tetrahydrofuran (a lithium atom in the initiator as a Lewis base). The equivalent of 15 times the stoichiometric ratio). After the temperature was raised to 50 ° C., 2.3 L of styrene was added for polymerization for 3 hours, then 23 L of isoprene was added for polymerization for 4 hours, and 2.3 L of styrene was further added for polymerization for 3 hours. 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-polyisoprene-polystyrene.
Subsequently, 10 kg of a triblock copolymer composed of polystyrene-polyisoprene-polystyrene was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was 5% by mass with respect to the copolymer. The reaction was carried out for 10 hours under the conditions of hydrogen pressure of 2 MPa and 150 ° C. After allowing to cool and release, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to give a hydrogenated product of a triblock copolymer consisting of polystyrene-polyisoprene-polystyrene (hereinafter, thermoplastic elastomer). (Referred to as (A1)). The resulting thermoplastic elastomer (A1) has a weight average molecular weight of 107,000, a styrene content of 21% by mass, a hydrogenation rate of 85%, a molecular weight distribution of 1.04, a 1,2-bond amount and 3,4. -The total amount of bonds was 60 mol%.

[Thermoplastic elastomer (A2)]
A pressure-resistant container purged with nitrogen and dried was charged with 150 L of cyclohexane as a solvent, 0.22 L of sec-butyllithium (10% by mass cyclohexane solution) as an initiator, and 0.3 L of tetrahydrofuran as a Lewis base (lithium atoms in the initiator). In contrast, the stoichiometric ratio was 14 times equivalent). After raising the temperature to 50 ° C., 0.72 L of styrene is added and polymerized for 3 hours. Subsequently, a mixed solution of 12.6 L of isoprene and 14.0 L of butadiene is added for polymerization for 4 hours, and 2.2 L of styrene is further added. For 3 hours. The obtained reaction liquid 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, 10 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, the palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to give a hydrogenated product of a triblock copolymer composed of polystyrene-poly (isoprene / butadiene) -polystyrene (hereinafter referred to as “polystyrene”). A thermoplastic elastomer (A2)). The resulting thermoplastic elastomer (A2) has a weight average molecular weight of 165,000, a styrene content of 13% by mass, a hydrogenation rate of 85%, a molecular weight distribution of 1.02, 1,2-bond amount and 3,4. -The total amount of bonds was 63 mol%.

[Thermoplastic elastomer (A3)]
A pressure-resistant vessel purged with nitrogen and dried was charged with 120 L of cyclohexane as a solvent, 0.12 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator, and 0.3 L of tetrahydrofuran as a Lewis base (lithium atoms in the initiator) The stoichiometric ratio is equivalent to 26 times). After the temperature was raised to 50 ° C., 3.6 L of styrene was added for polymerization for 3 hours, then 20.0 L of isoprene was added for polymerization for 4 hours, and further 3.6 L of styrene was added for polymerization for 3 hours. 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-polyisoprene-polystyrene.
Subsequently, 10 kg of a triblock copolymer composed of polystyrene-polyisoprene-polystyrene was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was 5% by mass with respect to the copolymer. The reaction was carried out for 10 hours under the conditions of hydrogen pressure of 2 MPa and 150 ° C. After allowing to cool and release, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to give a hydrogenated product of a triblock copolymer consisting of polystyrene-polyisoprene-polystyrene (hereinafter, thermoplastic elastomer). (Referred to as (A3)). The resulting thermoplastic elastomer (A3) has a weight average molecular weight of 320,000, a styrene content of 33% by mass, a hydrogenation rate of 90%, a molecular weight distribution of 1.07, a 1,2-bond amount and 3,4. -The total amount of bonds was 54 mol%.

[Thermoplastic elastomer (A4)]
A pressure-resistant container purged with nitrogen and dried was charged with 86 L of cyclohexane as a solvent, 0.22 L of sec-butyllithium (10% by mass cyclohexane solution) as an initiator, and 0.02 L of ethylene glycol dimethyl ether as a Lewis base (in the initiator). The equivalent of 0.7 times the stoichiometric ratio with respect to lithium atoms) was charged. After the temperature was raised to 50 ° C., 2.3 L of styrene was added for polymerization for 3 hours, subsequently, 25.5 L of butadiene was added for polymerization for 4 hours, and 2.3 L of styrene was further added for polymerization for 3 hours. 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-polybutadiene-polystyrene.
Subsequently, 10 kg of a triblock copolymer composed of polystyrene-polybutadiene-polystyrene is dissolved in 200 L of cyclohexane, and 5% by mass of palladium carbon (palladium supported amount: 5% by mass) is added to the copolymer as a hydrogenation catalyst. Then, the reaction was carried out for 10 hours under 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 product of a triblock copolymer composed of polystyrene-polybutadiene-polystyrene (hereinafter, thermoplastic elastomer ( A4)) was obtained. The resulting thermoplastic elastomer (A4) has a weight average molecular weight of 126,000, a styrene content of 21% by mass, a hydrogenation rate of 95%, a molecular weight distribution of 1.11 and a 1,2-bond content of 78 mol%. Met.

[Thermoplastic elastomer (A'5)]
Nitrogen-substituted and dried pressure vessel was charged with 80 L of cyclohexane as a solvent and 0.17 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator. After the temperature was raised to 50 ° C., 3.9 L of styrene was added and polymerized for 3 hours. Subsequently, a mixed solution of 12.1 L of isoprene and 10.9 L of butadiene was added for polymerization for 4 hours, and 3.9 L of styrene was further added. For 3 hours. The obtained reaction liquid 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 block-poly (isoprene / butadiene) block-polystyrene block. It was.
Subsequently, 20 kg of a triblock copolymer composed of polystyrene block-poly (isoprene / butadiene) block-polystyrene block was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5 mass%) was used as a hydrogenation catalyst. 5 mass% was added with respect to coalescence, and reaction was performed on the conditions of hydrogen pressure 2MPa and 150 degreeC for 10 hours. After cooling and releasing the pressure, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to hydrogenate a triblock copolymer composed of polystyrene block-poly (isoprene / butadiene) block-polystyrene block. A product (hereinafter referred to as a thermoplastic elastomer (A′5)) was obtained. The resulting thermoplastic elastomer (A'5) 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, a 1,2-bond amount and 3, 4- The total amount of bonds was 5 mol%.

[Polyvinyl acetal resin (B1)]
N-Butylaldehyde 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.

[Polar group-containing polypropylene resin (C1)]
42 g of polypropylene “Prime Polypro F327” (manufactured by Prime Polymer Co., Ltd.), 160 mg of maleic anhydride and 42 mg of 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane were added at 180 ° C. using a batch mixer. Melt kneading was performed under the condition of a screw rotation speed of 40 rpm. The obtained kneaded product (polar group-containing polypropylene resin (C1)) had an MFR [230 ° C., load 2.16 kg (21.18 N)] of 6 g / 10 min, maleic anhydride concentration of 0.3%, melting point Was 138 ° C.
The maleic anhydride concentration is a value obtained by titrating the obtained kneaded product with a methanol solution of potassium hydroxide, and the same applies hereinafter. The melting point is a value read from the endothermic peak of the differential scanning calorimetry curve when the temperature is raised at 10 ° C./min, and so on.

[Polypropylene resin (C'2)]
Polypropylene “Prime Polypro F327” (MFR [230 ° C., load 2.16 kg (21.18 N)]: 7 g / 10 min, manufactured by Prime Polymer Co., Ltd.) was used as the polypropylene resin (C′2).

[Polar group-containing polyethylene resin (C'3)]
Polyethylene “Neozex 0434N” (manufactured by Prime Polymer Co., Ltd.) 42 g, maleic anhydride 160 mg and 5-dimethyl-2,5-di (tertiary butyl peroxy) hexane 42 mg, 180 ° C. and screw rotation speed using a batch mixer Melt kneading was performed under the condition of 40 rpm. The obtained kneaded product (polar group-containing polyethylene resin (C′3)) had an MFR [190 ° C., load 2.16 kg (21.18 N)] of 2 g / 10 min and a maleic anhydride concentration of 0.3%. There was a melting point of 117 ° C.
[Softener (D1)]
Paraffinic process oil “Diana Process PW-90” (manufactured by Idemitsu Kosan Co., Ltd.) was used as the softening agent (D1).
[Tackifying resin (E1)]
Hydrogenated aromatic hydrocarbon resin “Regalite 1100” (softening point 100 ° C., manufactured by Eastman Chemical Co., Ltd.) was used as tackifying resin (E1).
[Tackifying resin (E2)]
Hydrogenated aromatic hydrocarbon resin “Regalite 1125” (softening point 123 ° C., manufactured by Eastman Chemical Co., Ltd.) was used as the tackifier resin (E2).
[Tackifying resin (E3)]
Hydrogenated terpene resin “Clearon M115” (softening point 115 ° C., manufactured by Yasuhara Chemical Co., Ltd.) was used as a tackifier resin (E3).
[Tackifying resin (E4)]
Hydrogenated terpene resin “Clearon P150” (softening point 152 ° C., manufactured by Yasuhara Chemical Co., Ltd.) was used as a tackifier resin (E4).

<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, evaluation of the insert adhesiveness and external appearance of the thermoplastic polymer composition of the adhesive body obtained in the following Examples or Comparative Examples was performed as follows.
(Insert adhesiveness)
A polyethylene terephthalate sheet is adhered to the thermoplastic polymer composition side of the adhesive prepared by the following method with an adhesive, and the insert is inserted in accordance with JIS K 6854-2 under the conditions of a peeling angle of 180 ° and a tensile speed of 50 mm / min. The adhesive strength between the part and the thermoplastic polymer composition was measured and used as an index of insert adhesiveness. The greater the adhesive strength, the better the insert adhesion.
(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 1-18 and Comparative Examples 1-4>
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 the temperature shown in Table 1 or 2 by heat conduction. Filling the CAV2 with a thermoplastic polymer composition having the composition shown in Table 1 or 2 under conditions of a mold temperature of 30 ° C. and a cylinder temperature of 230 ° C., immediately after the filling was started, the heater was turned off. The adhesive body was obtained by cooling the surface temperature of the adhesive body to 30 ° C. Tables 1 and 2 show the measurement results of the adhesive strength and the evaluation results of the appearance of the thermoplastic polymer composition of the obtained adhesive.

<Example 19>
In Example 1, the same operation was performed except that the heater was turned off 15 seconds after the filling of the thermoplastic polymer composition was started to obtain an adhesive.
Table 2 shows the measurement results of the adhesive strength and the evaluation results of the appearance of the thermoplastic polymer composition of the obtained adhesive.

From Table 1 and Table 2, by using a thermoplastic polymer composition containing specific components (A) to (C) at a specific compounding ratio, the temperature of the insert part at the time of insert molding is 190 ° C. or lower. Even if it is 140 degrees C or less, it turns out that it is excellent in the insert adhesiveness of the adhesive body obtained (Examples 1-19). 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 insert adhesiveness of the adhesive body obtained, and excellent in an external appearance (Examples 15-18). Moreover, insert adhesiveness was able to be improved further by hold | maintaining insert temperature for a fixed time after filling of a thermoplastic polymer composition (Example 19).
On the other hand, in the case of a thermoplastic polymer composition that deviates from the definition of the present invention, if the temperature of the insert part at the time of insert molding is 120 ° C., the insert adhesiveness is inferior. (Comparative Examples 1-3). 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 4).

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, a waterproof material, a design material or the like having an anti-slip function.
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 (10)

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,
Polymer block containing aromatic vinyl compound unit, and polymer containing isoprene unit, butadiene unit or isoprene / butadiene unit in which 1,2-bond amount and 3,4-bond amount are 40 mol% or more in total 1 to 100 parts by mass of a polyvinyl acetal resin (B) and a polar group-containing polypropylene resin (C) 5 with respect to 100 parts by mass of a block copolymer having a block or a hydrogenated product of the thermoplastic elastomer (A) The manufacturing method of an adhesive body which uses the thermoplastic polymer composition containing -100 mass parts, and makes the temperature of the insert components at the time of insert molding 30-150 degreeC.   In the thermoplastic polymer composition, the content of the component (B) is 5 to 70 parts by mass and the content of the component (C) is 5 to 70 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). The manufacturing method of the adhesive body of Claim 1 which exists.   The adhesive body according to claim 1 or 2, wherein the thermoplastic polymer composition further contains 0.1 to 300 parts by mass of a softening agent (D) with respect to 100 parts by mass of the thermoplastic elastomer (A). Production method.   The adhesion according to any one of claims 1 to 3, wherein the thermoplastic polymer composition further contains 1 to 100 parts by mass of a tackifier resin (E) with respect to 100 parts by mass of the thermoplastic elastomer (A). Body manufacturing method.   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%. The manufacturing method of the adhesive body as described in 2 ..   The manufacturing method of the adhesive body in any one of Claims 1-5 whose polar group containing polypropylene resin (C) is carboxylic acid modified polypropylene resin.   The manufacturing method of the adhesive body in any one of Claims 1-6 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 1-7 which controls the temperature of insert components with a heat generating body.   The method for producing an adhesive body according to claim 8, wherein the heating element is an electric heater, an electromagnetic induction heater, or a heat medium.   The manufacturing method of the adhesive body in any one of Claims 1-9 which uses a hot runner at the time of insert molding.