Resin compositions, molded articles, multilayer bodies and molded bodies

Abstract

To provide a resin composition capable of providing a molded article having excellent adhesiveness with another member and being molded from a resin composition containing a crystalline thermoplastic resin, and also provide a molded article molded from the resin composition, and a multi-layer body.SOLUTION: A resin composition for bonding contains a crystalline thermoplastic resin (A) and an acid-modified polymer (B), where the content of the crystalline thermoplastic resin (A) in the resin composition is more than the content of the acid-modified resin (B) in the resin composition, and the content of acid in the resin composition is 0.5 mass% or more.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a resin composition, a molded article, a multilayer body, and a molded body.

Background Art

[0002] Crystalline thermoplastic resins are easy to process and, furthermore, are excellent in mechanical physical properties, heat resistance, and other physical and chemical properties. Therefore, they are widely used in automotive parts, electrical and electronic equipment parts, and other precision equipment parts. In particular, polybutylene terephthalate resin is preferably used for injection molding because of its high crystallization rate.

[0003] For example, Patent Document 1 discloses a glass fiber reinforced polyester resin composition obtained by blending, per 100 parts by weight of a resin (A) mainly composed of a polyester comprising (a) 50 to 96% by weight of a polyester resin, (b) 35 to 3% by weight of a rubber-modified polystyrene resin, and (c) 15 to 1% by weight of an aromatic polycarbonate resin and / or a styrene-maleic anhydride copolymer, at least 10 to 150 parts by weight of glass fibers to which at least a sizing agent containing (B) an amino-based silane coupling agent and a novolak type epoxy resin is attached in part, and (C) 0.1 to 3 parts by weight of an epoxy compound.

[0004] Further, Patent Document 2 discloses a resin composition having a small shrinkage rate, which is characterized by blending (A) 25 to 90% by weight of a polybutylene terephthalate resin, (B) 25 to 1% by weight of a polyester resin other than polybutylene terephthalate having a crystallization temperature of 140 to 210°C, (C) 35 to 3% by weight of a rubber-modified polystyrene resin, and (D) at least one selected from an aromatic polycarbonate resin and a styrene-maleic anhydride copolymer in an amount of 15 to 1% by weight (where the total amount of (A) to (D) is 100% by weight).

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] Japanese Patent Publication No. 2006-016559 [Patent Document 2] Japanese Patent Publication No. 2006-219626 [Overview of the project] [Problems that the invention aims to solve]

[0006] Incidentally, in recent years, it has become common practice to bond molded products made from crystalline thermoplastic resins to other resin components using adhesives. The present invention aims to solve the aforementioned problems and to provide a resin composition that can provide a molded article formed from a resin composition containing a crystalline thermoplastic resin, which exhibits excellent adhesion to other components; a molded article formed from the resin composition; and a multilayer body. [Means for solving the problem]

[0007] Based on the above problems, the inventors conducted research and found that it is possible to improve adhesion by adjusting the amount of acid in the resin composition by blending an acid-modified polymer with a crystalline thermoplastic resin, thereby solving the above problems. Specifically, the above problem was solved by the following means. <1> A resin composition comprising a crystalline thermoplastic resin (A) and an acid-modified polymer (B), The content of the crystalline thermoplastic resin (A) in the resin composition is greater than the content of the acid-modified polymer (B) in the resin composition. An adhesive resin composition wherein the acid content in the resin composition is 0.5% by mass or more. <2> The crystalline thermoplastic resin (A) includes a crystalline thermoplastic polyester resin. <1> The adhesive resin composition described above. <3> The crystalline thermoplastic resin (A) includes a polybutylene terephthalate resin. <1> or <2> The adhesive resin composition described above. <4> The weight-average molecular weight of the acid-modified polymer (B) is 150,000 or more. <1> ~ <3> An adhesive resin composition as described in any one of the following. <5> The acid-modified polymer (B) includes a maleic anhydride polymer. <1> ~ <4> An adhesive resin composition as described in any one of the following. <6> The acid-modified polymer (B) includes a styrene-maleic anhydride polymer. <1> ~ <5> An adhesive resin composition as described in any one of the following. <7> Furthermore, the material includes an amorphous thermoplastic resin (C) other than the acid-modified polymer (B), <1> ~ <6> An adhesive resin composition as described in any one of the following. <8> The amorphous thermoplastic resin (C) includes a styrene-based resin. <7> The adhesive resin composition described above. <9> Furthermore, including an impact modifier, <1> ~ <8> An adhesive resin composition as described in any one of the following. <10> The impact modifier includes a core-shell elastomer. <9> The adhesive resin composition described above. <11> Furthermore, including reinforcing filler, <1> ~ <10> An adhesive resin composition as described in any one of the following. <12> The crystalline thermoplastic resin (A) comprises a polybutylene terephthalate resin, The acid-modified polymer (B) comprises a styrene-maleic anhydride polymer. Furthermore, it includes an amorphous thermoplastic resin (C) other than the acid-modified polymer (B), The amorphous thermoplastic resin (C) includes a styrene-based resin, Furthermore, including reinforcing filler, <1> ~ <11> An adhesive resin composition as described in any one of the following. <13> <1> ~ <12> A molded article formed from any one of the adhesive resin compositions described in the following. <14> A molded article formed from a resin composition containing a crystalline thermoplastic resin (A) and an acid-modified polymer (B), The molded product has other components that are bonded to it directly or at least via an adhesive, The content of the crystalline thermoplastic resin (A) in the resin composition is greater than the content of the acid-modified polymer (B) in the resin composition. A multilayer body wherein the acid content in the resin composition is 0.5% by mass or more. <15> The molded product and the other component are directly bonded together in some respects. <14> The multilayer described above. <16> The aforementioned multilayer body further includes an adhesive, The molded product and the other component are bonded together at least via an adhesive. <14> or <15> The multilayer described above. <17> The crystalline thermoplastic resin (A) includes a crystalline thermoplastic polyester resin. <14> ~ <16> A multilayer described in any one of the following. <18> The crystalline thermoplastic resin (A) includes a polybutylene terephthalate resin. <14> ~ <17> A multilayer described in any one of the following. <19> The weight-average molecular weight of the acid-modified polymer (B) is 150,000 or more. <14> ~ <18> A multilayer described in any one of the following. <20> The acid content in the resin composition is 1% by mass or more. <14> ~ <19> Multilayer described in any one of the following <21> The acid-modified polymer (B) includes a maleic anhydride polymer. <14> ~ <20> A multilayer described in any one of the following. <22> The acid-modified polymer (B) comprises a styrene-maleic anhydride polymer. <14> ~ <21> A multilayer described in any one of the following. <23> The arithmetic mean height (Sa) of the region of the molded product that is bonded to other components is 1.0 or greater. <14> ~ <22> A multilayer described in any one of the following. <24> The resin composition further comprises an amorphous thermoplastic resin (C) other than the acid-modified polymer (B). <14> ~ <23> A multilayer described in any one of the following. <25> The amorphous thermoplastic resin (C) includes a styrene-based resin. <24> The multilayer described above. <26> The aforementioned resin composition further comprises an impact modifier. <14> ~ <25> A multilayer described in any one of the following. <27> The impact modifier includes a core-shell elastomer. <26> The multilayer described above. <28>The multilayer body according to any one of <14> to <27>, wherein the resin composition further contains a reinforcing filler. <29>The multilayer body according to <28>, wherein the reinforcing filler contains glass. <30>The multilayer body according to any one of <14> to <32>, wherein the resin composition further contains a flame retardant. <31>The crystalline thermoplastic resin (A) contains a polybutylene terephthalate resin, the content of an acid in the resin composition is 1% by mass or more, the acid-modified polymer (B) contains a styrene - maleic anhydride polymer, the resin composition further contains an amorphous thermoplastic resin (C) other than the acid-modified polymer (B), the amorphous thermoplastic resin (C) contains a styrene resin, and the resin composition further contains glass fibers. The multilayer body according to any one of <14> to <30>. <32>The multilayer body according to <31>, wherein the resin composition further contains a core - shell elastomer. <33>A molded article containing the multilayer body according to any one of <14> to <32>.

Advantages of the Invention

[0008] According to the present invention, there are provided a resin composition capable of providing a molded article formed from a resin composition containing a crystalline thermoplastic resin and having excellent adhesiveness to other members, and a molded article formed from the resin composition.

Brief Description of the Drawings

[0009] [Figure 1] It is a schematic diagram showing a method for measuring the adhesive strength in an example.

Modes for Carrying Out the Invention

[0010] Hereinafter, modes for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the following present embodiment is an exemplification for explaining the present invention, and the present invention is not limited only to the present embodiment. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. In this specification, all physical properties and characteristic values ​​shall be those at 23°C unless otherwise specified. In this specification, unless otherwise specified, the weight-average molecular weight and number-average molecular weight are polystyrene-converted values ​​measured using GPC (gel permeation chromatography) with a Tosoh HLC-8320GPC EcoSEC, tetrahydrofuran as the solvent, three Shodex KF-G, KF-805L, and KF-800D columns, at a column temperature of 40°C and a flow rate of 1.2 mL / min, detected with a UV-8320 detector at a detection wavelength of 254 nm. If the standards described herein differ in measurement methods, etc., from year to year, unless otherwise specified, the standards as of January 1, 2021 shall apply.

[0011] The resin composition of this embodiment is a resin composition comprising a crystalline thermoplastic resin (A) and an acid-modified polymer (B), characterized in that the content of the crystalline thermoplastic resin (A) in the resin composition is greater than the content of the acid-modified polymer (B) in the resin composition, and the acid content in the resin composition is 0.5% by mass or more. It is presumed that by adjusting the amount of acid to be above a predetermined amount, a resin composition with excellent adhesion to other components can be obtained. Furthermore, in this embodiment, by blending an amorphous thermoplastic resin with a crystalline thermoplastic resin, and / or by using an amorphous thermoplastic resin as an acid-modified polymer, the molding shrinkage rate of the resin composition can be reduced, and the warping of the resulting molded product can be suppressed. In particular, the resin composition of this embodiment is preferably used as an adhesive resin composition. The multilayer body of this embodiment comprises a molded article formed from a resin composition containing a crystalline thermoplastic resin (A) and an acid-modified polymer (B), and other members bonded directly to the molded article, or at least via an adhesive, characterized in that the content of the crystalline thermoplastic resin (A) in the resin composition is greater than the content of the acid-modified polymer (B) in the resin composition, and the acid content in the resin composition is 0.5% by mass or more. It is presumed that by using a resin composition adjusted so that the amount of acid is above a predetermined amount, a multilayer body with excellent adhesion between the molded product obtained from the resin composition and other components can be obtained. Here, the molded product and the other component may be directly bonded together, or they may be bonded together at least via an adhesive. That is, because the molded product has excellent adhesive properties, it can be bonded to the other component itself without any adhesive. Furthermore, even when the molded product and the other component are bonded together at least via an adhesive, there are advantages such as the fact that they can be bonded sufficiently even without providing a primer layer. That is, the molded product and the other component may be bonded together using only an adhesive. Of course, the molded product and the other component may also be bonded together using a primer layer and an adhesive. In other words, the first embodiment of this model is a multilayer body in which a molded product and other components are directly bonded together in part. For example, the other components may be encapsulants or coatings (including paints and coatings) such as epoxy resin or silicone rubber. More specifically, the multilayer body of the first embodiment may be a multilayer body in which an encapsulant such as epoxy resin or silicone rubber is provided on the surface of a molded product, or a multilayer body in which a coating agent (including paints and coatings) is provided on the surface of a molded product. Furthermore, the multilayer body in this model may be a molded product made by a die molding method, and among these, it may be made by compression molding or transfer molding, or it may be a molded product made by welding, or it may be a multilayer body or molded product made by applying multiple liquids to the surface of a molded product, allowing them to react and harden. A second embodiment of this embodiment is a multilayer in which the multilayer further includes an adhesive, and the molded article and other components are bonded together at least via the adhesive. Examples include a multilayer in which a molded article formed from the resin composition of this embodiment is bonded to a component formed from metal with an adhesive, a multilayer in which a molded article formed from the resin composition of this embodiment is bonded to a component formed from glass with an adhesive, and a multilayer in which a molded article formed from the resin composition of this embodiment is bonded to a component formed from the resin composition of this embodiment or another resin composition with an adhesive. Furthermore, a multilayer may be in which a molded article formed from the resin composition of this embodiment is bonded to other components with a primer layer and an adhesive.

[0012] The molded articles, multilayers, or molded bodies in this embodiment are suitably used in electrical and electronic equipment, office automation equipment, portable information terminals, machine parts, home appliances, vehicle parts, various containers, lighting equipment, displays, and other components. Among these, they are particularly suitable for use in vehicle parts. In this embodiment, the molded body includes multilayers and may be either a component or a finished product. As described above, the molded product in this embodiment exhibits excellent adhesion to adhesives, sealants, decorative agents, coating agents (including paints and coatings), and other components. Therefore, it is preferably used in applications such as multilayer structures where the molded product is bonded to other components using adhesives, or in applications where the molded product is sealed, decorated, or coated using sealants, decorative agents, or coating agents. As mentioned above, "other components" refers to components made from thermoplastic resins, thermosetting resins, metals, glass, etc. Specifically, it is preferably used in ignition cases, sensor housings, ECU housings, fuel caps, window regulators, automotive connectors, relay cases, motor cases, various cases, various tubes, and the like.

[0013] An adhesive is a substance used to bond two objects together, and is usually not thermoplastic. It is preferable that the adhesive forms a layered structure (adhesive layer). The thickness of the adhesive layer is preferably 0.01 μm or more, more preferably 0.1 μm or more, and preferably 10,000 μm or less, and more preferably 5,000 μm or less. Examples of the adhesives mentioned above include silicone-based adhesives, modified silicone-based adhesives, epoxy-based adhesives, acrylic-based adhesives, urethane-based adhesives, and polyester-based adhesives. Only one type of adhesive may be used, or two or more types may be mixed and used.

[0014] The undercoat layer is a layer for further improving the adhesion between the adhesive and the molded product or other component, and the undercoat layer may be provided between the adhesive and the molded product or other component. The material used to form the undercoat layer can be referenced from Japanese Patent Application Publication No. 2022-123848, and this information is incorporated herein by reference.

[0015] Furthermore, as the sealing agent, sealing agents, sealing compositions, or sealing methods described in Japanese Patent Publication No. 2021-080363, Japanese Patent Publication No. 2014-062224, Japanese Patent Publication No. Hei 10-305444, Japanese Patent Publication No. 2011-018859, Japanese Patent Publication No. 2001-247746, and Japanese Patent Publication No. 2009-029842 can be suitably used, and the contents of these publications are incorporated herein by reference.

[0016] The following are specific examples of preferred configurations of the multilayer body according to this embodiment. It goes without saying that the multilayer body according to this embodiment is not limited to these examples. (1) A multilayer body having a molded article formed from a resin composition and other members, wherein the molded article and the other members are directly bonded together in part. (2) A multilayer having a molded article formed from a resin composition, an adhesive, and other components, wherein the molded article and the other components are bonded together via the adhesive. (3) A multilayer body comprising a molded article formed from a resin composition, a primer layer, an adhesive, and other components, wherein the primer layer is provided on at least a portion of the surface of the molded article, and the primer layer and the other components are bonded together via an adhesive. (4) A multilayer body comprising a molded article formed from a resin composition, an adhesive, a primer layer, and other members, wherein the primer layer is provided on at least a portion of the surface of the other members, and the primer layer and the molded article are bonded together via an adhesive.

[0017] It should be noted that the multilayer structure of this embodiment does not necessarily require each layer to be in the form of a flat plate, sheet, etc., and it goes without saying that it also includes, for example, an injection-molded product formed from the resin composition of this embodiment and an injection-molded product as another component bonded together with an adhesive.

[0018] In this embodiment, it is preferable that the arithmetic mean height (Sa) of the region of the molded product formed from the resin composition in this embodiment that is bonded to other components is 1.0 or higher. A higher Sa tends to improve adhesion to other components. It is sufficient that the above Sa is satisfied for the region of the molded product that is bonded to other components, but the entire surface of the molded product may also satisfy the above Sa. The aforementioned Sa is preferably 0.1 or higher, more preferably 0.5 or higher, even more preferably 0.6 or higher, even more preferably 0.8 or higher, and even more preferably 1.0 or higher. Furthermore, the upper limit of the aforementioned Sa is preferably 10.0 or lower, more preferably 5.0 or lower, even more preferably 4.0 or lower, even more preferably 3.0 or lower, even more preferably 2.5 or lower, and even more preferably 1.5 or lower. Setting it below the upper limit tends to further improve the appearance of the molded product. Means for making Sa 1.0 or higher include incorporating an acid-modified polymer (B) into the resin composition in this embodiment, incorporating a reinforcing filler, or combining two or more of these.

[0019] The arithmetic mean height (Sa) of the area of ​​a molded product formed from a resin composition that is bonded to another component can be calculated by observing it with a 10x objective lens of a hybrid laser microscope (LASERTEC OPTELICS HYBRID) and measuring the surface in accordance with ISO 25178 using the accompanying analysis software (Lasertec Microscope Solution Software LMeye7). For details, please refer to the description in the examples. Furthermore, the arithmetic mean height (Sa) of the surface of a molded product in a multilayer structure can be calculated by measuring the surface of the unjoined portion of the molded product, similar to the method described above. If there are no unjoined portions (regions), the value corresponding to the arithmetic mean height (Sa) can be obtained by observing and measuring the cross-section of the multilayer structure using an optical microscope or a scanning electron microscope.

[0020] Furthermore, in this embodiment, by blending an amorphous thermoplastic resin with a crystalline thermoplastic resin in the resin composition, and / or by using an amorphous thermoplastic resin as an acid-modified polymer, the molding shrinkage rate of the resin composition can be reduced, and the warping of the resulting molded product can be suppressed. The details of the resin composition in this embodiment will be described below.

[0021] <Crystalline thermoplastic resin (A)> The resin composition in this embodiment includes a crystalline thermoplastic resin. In this embodiment, a crystalline resin refers to a resin that exhibits a clear melting point by DSC (Differential Scanning Calorimetry) measurement. A resin that does not exhibit a clear melting point is defined as an amorphous thermoplastic resin. Examples of crystalline thermoplastic resins include polyamide resins, polyacetal resins, and crystalline thermoplastic polyester resins. Polyamide resins and crystalline thermoplastic polyester resins (hereinafter sometimes simply referred to as "polyester resins") are preferred, crystalline thermoplastic polyester resins are more preferred, and polybutylene terephthalate resins are even more preferred. Furthermore, in this invention, an acid-modified polymer that corresponds to a crystalline thermoplastic resin is defined as acid-modified polymer (B).

[0022] Details of the polyamide resin can be found in paragraphs 0012 to 0022 of Japanese Patent Publication No. 2020-100832, which are incorporated herein by reference. Details of the polyacetal resin can be found in paragraphs 0009 to 0014 of Japanese Patent Publication No. 2021-098767, which are incorporated herein by reference.

[0023] Polyester resin is a polyester obtained by polycondensation of dicarboxylic acid compounds and dihydroxy compounds, polycondensation of oxycarboxylic acid compounds, or polycondensation of these compounds, and may be either homopolyester or copolyester.

[0024] As the dicarboxylic acid compound constituting the polyester resin, aromatic dicarboxylic acids or their ester-forming derivatives are preferably used. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylisopropylidene-4,4'-dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p-tert-phenylene-4,4'-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, etc., with terephthalic acid being preferred.

[0025] These aromatic dicarboxylic acids may be used in combination of two or more types. As is well known, they can be used in polycondensation reactions not only as free acids but also as ester-forming derivatives such as dimethyl esters. Furthermore, in small amounts, these aromatic dicarboxylic acids can be used in combination with one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedionic acid, and sebacic acid, or alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

[0026] Examples of dihydroxy compounds constituting the polyester resin include aliphatic diols such as ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, 2-methylpropane-1,3-diol, diethylene glycol, and triethylene glycol, as well as alicyclic diols such as cyclohexane-1,4-dimethanol, and mixtures thereof. In small amounts, one or more long-chain diols with molecular weights of 400 to 6,000, such as polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol, may be copolymerized. In addition, aromatic diols such as hydroquinone, resorcinol, naphthalenediol, dihydroxydiphenyl ether, and 2,2-bis(4-hydroxyphenyl)propane can also be used.

[0027] In addition to the difunctional monomers mentioned above, small amounts of trifunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane can also be used to introduce branched structures, as well as monofunctional compounds such as fatty acids to adjust molecular weight. The polyester resin used is typically one that consists mainly of a polycondensation of a dicarboxylic acid and a diol, that is, one in which 50% by mass, preferably 70% by mass or more of the total polyester resin consists of this polycondensate. Aromatic carboxylic acids are preferred as the dicarboxylic acid, and aliphatic diols are preferred as the diol.

[0028] Of these, polyalkylene terephthalates in which 95 mol% or more of the acid component is terephthalic acid and 95% by mass or more of the alcohol component is an aliphatic diol are preferred. Typical examples are polybutylene terephthalate resin and polyethylene terephthalate resin, with polybutylene terephthalate resin being preferred. These are preferably close to homopolyesters, that is, 95% by mass or more of the total resin consists of the terephthalic acid component and the 1,4-butanediol or ethylene glycol component. Furthermore, copolymers containing isophthalic acid, dimer acid, polyalkylene glycols such as polytetramethylene glycol (PTMG) are also preferred. Examples of these copolymers include those in which the copolymerization amount is 1 mol% or more and less than 50 mol% of the total segments of polyalkylene terephthalate.

[0029] The concentration of terminal carboxyl groups in the polyester resin is preferably 1 to 23 eq / ton, and more preferably 7 to 20 eq / ton. This range tends to improve fluidity. In this embodiment, if the resin composition contains two or more polyester resins, the concentration of terminal carboxyl groups of the polyester resins shall be that of the mixture. The amount of terminal carboxyl groups can be determined by dissolving 0.5 g of polyester resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / L benzyl alcohol solution of sodium hydroxide.

[0030] The resin composition in this embodiment preferably contains 30% by mass or more of a crystalline thermoplastic resin (preferably a polyester resin, more preferably a polybutylene terephthalate resin) of the total resin components, more preferably 75% by mass or more, and more preferably 70% by mass or less. The resin composition in this embodiment may contain only one type of crystalline thermoplastic resin, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0031] <Acid-modified polymer (B)> The resin composition in this embodiment includes an acid-modified polymer. The inclusion of the acid-modified polymer enhances adhesion to other components. The acid-modified polymer (B) may be a crystalline resin or an amorphous resin, but it is usually an amorphous resin. By using an amorphous resin, low warping can be effectively achieved. Furthermore, the acid-modified polymer may be a thermoplastic resin or a thermosetting resin, but it is preferably a thermoplastic resin.

[0032] The acid-modified polymer may consist only of acid group-containing monomer units, but it is preferable that it contains other monomer units in addition to acid group-containing monomer units. Preferably, it contains at least one of aromatic vinyl group-containing monomer units and olefin group-containing monomer units in addition to acid group-containing monomer units (preferably maleic anhydride group-containing monomer units). More preferably, it contains at least one of styrene group-containing monomer units and olefin group-containing monomer units in addition to acid-modified monomer units, and even more preferably, it contains styrene group-containing monomer units in addition to acid-modified monomer units. Including styrene monomer units in addition to acid-modified monomer units tends to significantly improve not only adhesion but also low warpage.

[0033] Examples of aromatic vinyl monomers include styrene sulfonates such as styrene, sodium styrenesulfonate, and ammonium styrenesulfonate; styrene sulfonate esters such as ethyl styrenesulfonate; styrene alkyl ethers such as t-butoxystyrene; styrene derivatives such as acetoxystyrene and vinylbenzoic acid; and α-methylstyrene and α-methylstyrene derivatives. These may be used individually or in combination of two or more. Examples of olefin monomers include α-olefins such as ethylene and propylene. These may be used individually or in combination of two or more. The content of aromatic vinyl monomer units and / or olefin monomers in the acid-modified polymer is preferably 2% by mass or more, and preferably 98% by mass or less.

[0034] The acid-modified polymer may contain other monomer units in addition to those mentioned above. Preferred other monomers include acrylic monomers and maleimide monomers. Examples of acrylic monomers include methyl methacrylate and methyl acrylate. Examples of maleimide monomers include maleimide monomers such as N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide. Acrylonitrile is also an example. The acid modification of the acid-modified polymer is preferably carried out with an acid and / or anhydride, and more preferably with an acid anhydride. Specifically, the acid modification of the polymer is preferably carried out with an organic acid and its acid anhydride, more preferably with carboxylic acids and carboxylic anhydrides, even more preferably with maleic acid and maleic anhydride, and even more preferably with maleic anhydride.

[0035] The proportion of acid modification (acid content) in the acid-modified polymer is preferably 1% by mass or more, preferably 2% by mass or more, preferably 5% by mass or more, preferably 50% by mass or less, more preferably 35% by mass or less, and may also be 25% by mass or less, or 10% by mass or less. The acid content in the acid-modified polymer within a resin composition can be calculated by dissolving the resin composition in a soluble solvent, evaporating the solvent from the resulting solution, dissolving the remaining substance (residue) in a deuterated solvent for NMR measurement, and then calculating the acid content by NMR measurement. If acid groups cannot be detected by NMR measurement, the residual substance can also be dissolved in a soluble solvent, an indicator is added, and the acid content can be calculated by titration with a basic solvent. The aforementioned soluble solvent and the solvent used for NMR measurement are preferably solvents in which the resin component in the composition is soluble, and examples include, but are not limited to, dichloromethane, methanol, and chloroform.

[0036] Specific examples of the maleic anhydride-modified polymer used in this embodiment are more preferably at least one of styrene-maleic anhydride polymer, styrene-N-phenylmaleimide-maleic anhydride polymer, and α-olefin-maleic anhydride polymer, and more preferably styrene-maleic anhydride polymer. In this embodiment, it is preferable that the acid-modified polymer used is configured such that the sum of the acid group monomer units, aromatic vinyl group-containing monomer units, and other monomer units added as needed accounts for 100% by mass of the total of all constituent units excluding terminal groups.

[0037] The acid-modified polymer may also be an acid-modified impact modifier. The acid-modified impact modifier that can be used in this embodiment is at least one acid-modified elastomer consisting of an acid-modified olefin-based elastomer and an acid-modified styrene-based elastomer.

[0038] As for the olefin-based elastomer, it is sufficient to have a polyolefin portion in the soft phase, and ethylene propylene rubber such as EPR and EPDM can be preferably used.

[0039] Styrene-based elastomers typically consist of a styrene component and an elastomer component, with the styrene component usually present in a proportion of 5 to 80% by mass, preferably 10 to 50% by mass, and particularly preferably 15 to 30% by mass. Examples of elastomer components include conjugated diene hydrocarbons such as butadiene, isoprene, and 1,3-pentadiene. More specifically, styrene-based elastomers include styrene-butadiene copolymer (SBS) elastomers and styrene-isoprene copolymer (SIS) elastomers.

[0040] In this embodiment, the acid modification of the acid-modified impact modifier refers to introducing cyclic anhydrides or carboxylic acid groups into the copolymer side chains using cyclic acid anhydrides such as maleic anhydride, phthalic anhydride, glutaric anhydride, or succinic anhydride. Acid denaturation can be introduced using commonly performed methods, such as graft copolymerization and random copolymerization. Examples of such acid-modified impact modifiers include Asahi Kasei's "ToughTec M1913," Arkema's "Rotada 4613," and Mitsui Chemicals' "Toughmer MP0610."

[0041] The weight-average molecular weight of the acid-modified polymer is preferably 50,000 or more, more preferably 80,000 or more, even more preferably 90,000 or more, even more preferably 100,000 or more, and even more preferably 150,000 or more. Setting it above the lower limit tends to improve compatibility with the polyester resin and improve the surface appearance. Furthermore, the weight-average molecular weight of the acid-modified polymer is preferably 500,000 or less, more preferably 400,000 or less, even more preferably 300,000 or less, and even more preferably 200,000 or less. Setting it below the upper limit tends to increase the probability of the acid-modified polymer, and consequently the acid (acid group), being present on the surface of the resulting molded product, and further improve the adhesion of the resin composition. The weight-average molecular weights mentioned above are polystyrene-based weight-average molecular weights measured by gel permeation chromatography (GPC) using tetrahydrofuran as the solvent. In this embodiment, if the resin composition contains two or more acid-modified polymers, the weight-average molecular weight of the mixture is used.

[0042] In this embodiment, the acid value of the acid-modified polymer is greater than 0 mgKOH / g, preferably 0.5 mgKOH / g or more, more preferably 2 mgKOH / g or more, even more preferably 5 mgKOH / g or more, and even more preferably 10 mgKOH / g or more. Depending on the application, it may be 15 mgKOH / g or more. Setting it above the lower limit allows for more effective suppression of the decomposition of the polyester resin. Furthermore, the upper limit of the acid value of the acid-modified polymer is preferably 100 mgKOH / g or less, more preferably 90 mgKOH / g or less, and even more preferably 80 mgKOH / g or less. Depending on the application, it may be 70 mgKOH / g or less, 60 mgKOH / g or less, 50 mgKOH / g or less, 40 mgKOH / g or less, or 35 mgKOH / g or less. Setting it below the upper limit tends to effectively suppress the deterioration of the mechanical properties of the molded product. If the resin composition in this embodiment contains two or more acid-modified polymers, the acid value shall be the acid value of the mixture.

[0043] In this embodiment, the content of the acid-modified polymer in the resin composition is less than that of the crystalline thermoplastic resin; that is, the content of the acid-modified polymer in the resin composition is greater than that of the crystalline thermoplastic resin. More specifically, the content is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and may be 6 parts by mass or more, 10 parts by mass or more, 16 parts by mass or more, or 20 parts by mass or more, per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). Setting the content above the lower limit increases the probability of maleic acid being present on the surface of the molded product, and tends to improve the adhesion of the resulting molded product to other components. Furthermore, the upper limit of the content of the acid-modified polymer is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and may be 45 parts by mass or less, or 30 parts by mass or less, per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). Setting the content below the upper limit tends to improve the heat resistance of the resin composition. The resin composition in this embodiment may contain only one type of acid-modified polymer, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0044] In this embodiment, the acid content in the resin composition is 0.5% by mass or more. By setting it above the lower limit, excellent adhesion of the resulting molded product to other components can be achieved. The acid content in the resin composition is preferably 0.55% by mass or more, more preferably 0.60% by mass or more, even more preferably 0.70% by mass or more, even more preferably 1.0% by mass or more, and even more preferably 1.4% by mass or more. Furthermore, the upper limit of the acid content in the resin composition is preferably 10.0% by mass or less, more preferably 8.0% by mass or less, even more preferably 6.0% by mass or less, even more preferably 4.0% by mass or less, even more preferably 3.0% by mass or less, even more preferably 2.5% by mass or less, and even more preferably 2.0% by mass or less. Setting it below the upper limit tends to further improve the basic physical properties and surface appearance of the molded product. In particular, when the acid content is 1.4% by mass or more and 2.5% by mass or less, and the arithmetic mean height (Sa) is 1.0 or more and 2.5 or less, it is preferable because it provides a good balance between excellent adhesion to other components, the basic physical properties of the resin composition, and the surface appearance. The acid content in the resin composition can be calculated by multiplying the acid content of the acid-modified polymer in 100 parts by mass of the resin composition by the acid content of the acid-modified polymer, provided that the acid content of the acid-modified polymer is known through measurement or other means. Furthermore, if the acid content in the acid-modified polymer is unknown, as described above, the resin composition is dissolved in a soluble solvent, the solvent is evaporated from the resulting solution, and the remaining substance (residue) is dissolved in a deuterated solvent for NMR measurement. The acid content is then calculated by NMR measurement. If acid groups cannot be confirmed by NMR measurement, the residual substance can also be dissolved in a soluble solvent, an indicator is added, and the acid content is calculated by titration with a basic solvent.

[0045] <Amorphous thermoplastic resins other than acid-modified polymers (C)> In this embodiment, the resin composition preferably includes an amorphous thermoplastic resin (C) other than the acid-modified polymer (B). By including an amorphous thermoplastic resin, warping of the resulting molded product can be effectively suppressed. This is presumed to be because amorphous thermoplastic resins shrink less during molding than crystalline thermoplastic resins. Furthermore, in this embodiment, by including an amorphous thermoplastic resin, an appropriate roughness can be easily formed on the surface of the molded product using chemicals, etc., thereby further improving the adhesion of the resulting molded product. Examples of amorphous thermoplastic resins include styrene-based resins such as polystyrene resin, high-impact polystyrene resin (HIPS), hydrogenated polystyrene resin, polyacrylic styrene resin, ABS resin (acrylonitrile butadiene styrene resin), AS resin (acrylonitrile styrene resin), AES resin (acrylonitrile ethylene rubber styrene resin), and ASA resin (acrylonitrile styrene acrylic rubber resin), as well as polyalkyl methacrylate resin, (meth)acrylate copolymer, polymethacrylate methacrylate resin, polyphenyl ether resin, polycarbonate resin, amorphous polyalkylene terephthalate resin, amorphous polyester resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, amorphous polyarylate resin, and polyethersulfone resin. Styrene-based resins and polycarbonate resins are preferred, with styrene-based resins being more preferred. Using styrene-based resins tends to more effectively improve the molding stability and thermal stability of the resin composition.

[0046] Among styrene-based resins, high-impact polystyrene resin (HIPS), ABS resin (acrylonitrile butadiene styrene resin), and AS resin (acrylonitrile styrene resin) are preferred, with high-impact polystyrene resin (HIPS) and AS resin (acrylonitrile styrene resin) being more preferred.

[0047] In this embodiment, the content of amorphous thermoplastic resin (preferably styrene-based resin) in the resin composition is preferably 1 part by mass or more, may be 5 parts by mass or more, may be 10 parts by mass or more, may be 20 parts by mass or more, or may be 25 parts by mass or more, per 100 parts by mass of crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). Setting it above the lower limit tends to effectively suppress warping of the resulting molded product. Furthermore, the upper limit of the content of amorphous thermoplastic resin (preferably styrene-based resin) is preferably 90 parts by mass or less, preferably 80 parts by mass or less, preferably 60 parts by mass or less, more preferably 55 parts by mass or less, and may be 45 parts by mass or less, per 100 parts by mass of crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). The resin composition of the embodiment may contain only one amorphous thermoplastic resin or two or more amorphous thermoplastic resins. When two or more amorphous thermoplastic resins are included, it is preferable that the total amount is within the above range.

[0048] In this embodiment, the resin composition preferably contains an acid-modified polymer and an amorphous thermoplastic resin in a total amount of 35 parts by mass or more, preferably 90 parts by mass or less, and may also be 55 parts by mass or less, or 45 parts by mass or less, per 100 parts by mass of crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin).

[0049] <Epoxy group-containing compound (D)> The resin composition in this embodiment preferably contains an epoxy group-containing compound. The epoxy group-containing compound can effectively suppress the hydrolysis of crystalline thermoplastic resins, particularly polybutylene terephthalate resins, which causes a decrease in molecular weight and a decrease in mechanical strength, etc.

[0050] In this embodiment, it is preferable to use an epoxy group-containing compound with a weight-average molecular weight (Mw) of 200 to 10000. Mw is preferably 9000 or less, more preferably 6000 or less, most preferably 4000 or less, especially 2000 or less, and most preferably 1000 or less.

[0051] Any epoxy group-containing compound will suffice, as long as it has one or more epoxy groups in one molecule. Typically, glycidyl compounds, which are reaction products of alcohols, phenols, or carboxylic acids with epichlorohydrin, or compounds in which an olefinic double bond has been epoxidized, can be used. Examples of epoxy group-containing compounds include novolac-type epoxy compounds, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, alicyclic epoxy compounds, glycidyl ethers, glycidyl esters, epoxidized butadiene polymers, and resorcinol-type epoxy compounds.

[0052] Examples of novolac-type epoxy compounds include phenol novolac-type epoxy compounds and cresol novolac-type epoxy compounds. Examples of bisphenol A-type epoxy compounds include bisphenol A-diglycidyl ether and hydrogenated bisphenol A-diglycidyl ether, and examples of bisphenol F-type epoxy compounds include bisphenol F-diglycidyl ether and hydrogenated bisphenol F-diglycidyl ether.

[0053] Examples of alicyclic epoxy compounds include vinylcyclohexene dioxide, dicyclopentadiene oxide, 3,4-epoxycyclohexyl-3,4-cyclohexyl carboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, and 3,4-epoxycyclohexyl glycidyl ether.

[0054] Specific examples of glycidyl ethers include monoglycidyl ethers such as methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, and allyl glycidyl ether; and diglycidyl ethers such as neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, and bisphenol A diglycidyl ether.

[0055] Examples of glycidyl esters include monoglycidyl esters such as glycidyl benzoate and glycidyl sorbate; and diglycidyl esters such as diglycidyl adipic acid, diglycidyl terephthalate, and diglycidyl orthophthalate.

[0056] Examples of epoxidized butadiene polymers include epoxidized polybutadiene, epoxidized styrene-butadiene copolymers, and epoxidized hydrogenated styrene-butadiene copolymers. Examples of resorcinol-type epoxy compounds include resorcinol diglycidyl ether.

[0057] The epoxy group-containing compound may be a copolymer in which a glycidyl group-containing compound is one of the components. For example, a copolymer of a glycidyl ester of an α,β-unsaturated acid and one or more monomers selected from the group consisting of α-olefins, acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters may be used.

[0058] The epoxy equivalent of the epoxy group-containing compound is preferably 150 to 1000 g / eq. By setting the epoxy equivalent to 150 g / eq or more, the viscosity of the resin composition can be moderately lowered, and by setting the epoxy equivalent to 1000 g / eq or less, the amount of epoxy groups is reduced, which tends to further improve the hydrolysis resistance of the polybutylene terephthalate resin. The epoxy equivalent is more preferably 160 to 800 g / eq, even more preferably 170 to 700 g / eq, and even more preferably 180 to 650 g / eq.

[0059] As epoxy group-containing compounds, bisphenol A-type epoxy compounds and novolac-type epoxy compounds obtained from the reaction of bisphenol A or novolac with epichlorohydrin are particularly preferred because they easily improve hydrolysis resistance and alkali resistance, and also from the viewpoint of the surface appearance of the molded product.

[0060] In this embodiment, if the resin composition contains an epoxy group-containing compound, its content is preferably 0.1 parts by mass or more, more preferably 0.15 parts by mass or more, even more preferably 0.2 parts by mass or more, and even more preferably 0.25 parts by mass or more, per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). Setting the content above the lower limit tends to further improve the hydrolysis resistance of the resulting molded article. Furthermore, the upper limit of the epoxy group-containing compound content is preferably 4 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). Setting the content below the upper limit tends to further improve the fluidity of the resin composition. The resin composition of the embodiment may contain only one epoxy group-containing compound, or it may contain two or more. When it contains two or more, it is preferable that the total amount is within the above range.

[0061] <Release agent (E)> The resin composition in this embodiment preferably contains a mold release agent. A wide range of known release agents can be used, and low molecular weight polyolefins or esterified aliphatic carboxylic acids are preferred. Examples of low molecular weight polyolefins include those with a weight-average molecular weight of 10,000 or less, preferably 5,000 or less, and even more preferably 1,000 or less. The esterified aliphatic carboxylic acid is preferably an ester of a polyhydric alcohol and an aliphatic carboxylic acid having 10 to 19 carbon atoms. Regarding release agents, specific examples can be found in paragraphs 0063 to 0077 of Japanese Patent Publication No. 2018-070722 and paragraphs 0090 to 0098 of Japanese Patent Publication No. 2019-123809, the contents of which are incorporated herein by reference.

[0062] If the resin composition in this embodiment contains a release agent, the content is preferably 0.01 parts by mass or more, more preferably 0.08 parts by mass or more, and even more preferably 0.2 parts by mass or more, per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). Furthermore, the upper limit of the release agent content is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, even more preferably 1 part by mass or less, and even more preferably 0.8 parts by mass or less, per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). The resin composition in this embodiment may contain only one type of release agent or two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0063] <Impact modifier (F)> The resin composition in this embodiment may also preferably contain an impact modifier. The impact resistance of the resin composition can be improved by including an impact modifier.

[0064] The impact modifier that can be used in this embodiment is preferably a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component that can copolymerize with it. The graft copolymer may be produced by any of the following methods: bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., and the copolymerization method may be single-stage grafting or multi-stage grafting. In the case of an acid-modified impact modifier, it is considered to be an acid-modified polymer (B) in this specification.

[0065] The rubber component has a glass transition temperature of 0°C or lower, preferably -20°C or lower, and more preferably -30°C or lower. Specific examples of rubber components include polybutadiene rubber, polyisoprene rubber, polyalkyl acrylate rubber such as polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate-2-ethylhexyl acrylate copolymer, silicone rubber such as polyorganosiloxane rubber, butadiene-acrylic composite rubber, IPN (Interpenetrating Polymer Network) type composite rubber consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-α-olefin rubber such as ethylene-propylene rubber, ethylene-butene rubber, and ethylene-octene rubber, ethylene-acrylic rubber, and fluororubber. These may be used individually or in mixtures of two or more. Among these, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN-type composite rubber consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferred in terms of mechanical properties and surface appearance.

[0066] Graft copolymers obtained by copolymerizing rubber components are preferably core-shell elastomers in terms of impact resistance and surface appearance. Among these, core-shell elastomers are particularly preferred, comprising a core layer made of at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, and IPN-type composite rubber consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, and a shell layer formed by copolymerizing (meth)acrylic acid ester around it. In the above core-shell elastomer, it is preferable that the rubber component is contained in 40% by mass or more, and more preferably 60% by mass or more. Furthermore, it is preferable that the (meth)acrylic acid is contained in 10% by mass or more. It should be noted that the core-shell elastomer in this embodiment does not necessarily have to have a clearly distinguishable core layer and shell layer, and is intended to broadly include compounds obtained by graft polymerization of rubber components around the core portion.

[0067] Preferred specific examples of core-shell elastomers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic butadiene rubber copolymer, methyl methacrylate-acrylic butadiene rubber-styrene copolymer, and methyl methacrylate-(acrylic silicone IPN rubber) copolymer.

[0068] Examples of such impact modifiers include "Paraloid (registered trademark, hereinafter the same) EXL2602", "Paraloid EXL2603", "Paraloid EXL2655", "Paraloid EXL2311", "Paraloid EXL2313", "Paraloid EXL2315", "Paraloid KM330", "Paraloid KM336P", and "Paraloid KCZ201" from Rohm & Haas Japan; "Metabren (registered trademark, hereinafter the same) C-223A", "Metabren E-901", "Metabren S-2001", and "Metabren SRK-200" from Mitsubishi Rayon Corporation; "KaneAce (registered trademark, hereinafter the same) M-511", "KaneAce M-600", "KaneAce M-400", "KaneAce M-580", "KaneAce M-711", and "KaneAce MR-01" from Kaneka Corporation; and "UBESTA XPA" from Ube Industries.

[0069] If the resin composition in this embodiment contains an impact modifier, its content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 8 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 12 parts by mass or more, per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). Setting the content above the lower limit tends to further improve the impact resistance of the resulting molded product. Furthermore, the upper limit of the impact modifier content is preferably 30 parts by mass or less, more preferably 28 parts by mass or less, even more preferably 26 parts by mass or less, even more preferably 24 parts by mass or less, and even more preferably 22 parts by mass or less, per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). Setting the content below the upper limit tends to further improve the fluidity of the resin composition. The resin composition of the embodiment may contain only one impact modifier or two or more impact modifiers. When two or more impact modifiers are included, it is preferable that the total amount is within the above range. It's nice.

[0070] <Stabilizer (G)> The resin composition in this embodiment may contain a stabilizer. Examples of stabilizers include hindered phenol compounds, hindered amine compounds, phosphorus compounds, and sulfur-based stabilizers. Among these, phosphorus compounds are preferred. Specifically, as stabilizers, reference can be made to paragraphs 0067-0075 of Japanese Patent Publication No. 2021-063196, paragraphs 0046-0057 of Japanese Patent Publication No. 2018-070722, paragraphs 0030-0037 of Japanese Patent Publication No. 2019-056035, and paragraphs 0066-0078 of International Publication No. 2017 / 038949, the contents of which are incorporated herein by reference.

[0071] If the resin composition in this embodiment contains a stabilizer, the content is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.08 parts by mass or more, per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). Furthermore, the upper limit of the stabilizer content is preferably 3 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.5 parts by mass or less, and even more preferably 0.3 parts by mass or less, per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). The resin composition in this embodiment may contain only one stabilizer or two or more stabilizers. When two or more stabilizers are included, it is preferable that the total amount is within the above range.

[0072] <Coloring agent (H)> The resin composition in this embodiment may contain a coloring agent. The coloring agent may be a dye or a pigment, but a pigment is preferred. The coloring agent may be either an organic or inorganic coloring agent. Furthermore, it may be either a chromatic or achromatic coloring agent. Examples of colorants include those described in paragraphs 0121 to 0123 of Japanese Patent Publication No. 2021-101020 and paragraphs 0088 to 0090 of Japanese Patent Publication No. 2019-188393, the contents of which are incorporated herein by reference. The resin composition in this embodiment preferably contains carbon black. There are no restrictions on the type, raw material, or manufacturing method of the carbon black; furnace black, channel black, acetylene black, Ketjen black, etc., can be used. There are no particular restrictions on the number-average particle size, but it is preferably about 5 to 60 nm.

[0073] Carbon black is preferably formulated as a masterbatch pre-mixed with a thermoplastic resin, preferably a polybutylene terephthalate resin.

[0074] When the resin composition in this embodiment contains a coloring agent (preferably carbon black), the content is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). Setting the content above the lower limit allows the coloring effect to be more effectively exhibited. Furthermore, the upper limit of the coloring agent content is preferably 4 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin). Setting the content below the upper limit tends to further improve the mechanical strength of the resulting molded product. The resin composition in this embodiment may contain only one colorant or two or more. When two or more colorants are included, it is preferable that the total amount is within the above range.

[0075] <Reinforced filler (I)> The resin composition in this embodiment preferably contains a reinforcing filler. By including a reinforcing filler, the mechanical strength of the resulting molded product can be increased. The reinforcing filler that can be used in this embodiment is not particularly specified in terms of type, and may be any of the following: fibers, fillers, beads, etc., but fibers are preferred.

[0076] If the reinforcing filler is made of fibers, it may be short fibers or long fibers. The raw materials for the reinforcing filler include inorganic materials such as glass, carbon (carbon fiber, etc.), alumina, boron, ceramics, and metals (steel, etc.), and organic materials such as plants (including kenaf, bamboo, etc.), aramid, polyoxymethylene, aromatic polyamide, poly(p-phenylenebenzobisoxazole), and ultra-high molecular weight polyethylene, with glass being preferred.

[0077] In this embodiment, the resin composition preferably contains glass fibers as a reinforcing filler. The glass fibers are selected from glass compositions such as A glass, C glass, E glass, R glass, D glass, M glass, and S glass, with E glass (alkali-free glass) being particularly preferred. Glass fibers refer to fibrous materials whose cross-sectional shape, when cut perpendicular to the length, is circular or polygonal. Glass fibers typically have a number-average fiber diameter of 1 to 25 μm, preferably 5 to 17 μm. A number-average fiber diameter of 1 μm or more tends to improve the moldability of the resin composition. A number-average fiber diameter of 25 μm or less tends to improve the appearance of the resulting structure and enhance its reinforcing effect. Glass fibers may be single fibers or multiple single fibers twisted together. The glass fibers may take any form, such as glass roving made by continuously winding single fibers or multiple strands twisted together, chopped strands cut to a length of 1 to 10 mm (i.e., glass fibers with a number-average fiber length of 1 to 10 mm), or milled fibers crushed to a length of approximately 10 to 500 μm (i.e., glass fibers with a number-average fiber length of 10 to 500 μm), but chopped strands cut to a length of 1 to 10 mm are preferred. Glass fibers with different forms can also be used in combination. Furthermore, glass fibers having an irregular cross-sectional shape are also preferred. This irregular cross-sectional shape refers to a flattening ratio, which is indicated by the major axis / minor axis ratio of the cross-section perpendicular to the length direction of the fiber, and is, for example, 1.5 to 10, more preferably 2.5 to 10, even more preferably 2.5 to 8, and particularly preferably 2.5 to 5.

[0078] The glass fibers may be surface-treated with, for example, silane compounds, epoxy compounds, or urethane compounds, or oxidized, in order to improve their affinity with the resin components, as long as the properties of the resin composition in this embodiment are not significantly impaired.

[0079] The resin composition in this embodiment preferably contains 10 parts by mass or more of a reinforcing filler (preferably glass fiber) per 100 parts by mass of a crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin), more preferably 20 parts by mass or more, even more preferably 35 parts by mass or more, even more preferably 45 parts by mass or more, and even more preferably 55 parts by mass or more. By setting the amount above the lower limit, the mechanical strength of the resulting structure tends to increase further. Furthermore, the content of the reinforcing filler (preferably glass fiber) per 100 parts by mass of the crystalline thermoplastic resin (preferably polyester resin, more preferably polybutylene terephthalate resin) is preferably 300 parts by mass or less, more preferably 270 parts by mass or less, even more preferably 250 parts by mass or less, even more preferably 200 parts by mass or less, even more preferably 170 parts by mass or less, even more preferably 150 parts by mass or less, even more preferably 100 parts by mass or less, even more preferably 90 parts by mass or even more preferably 80 parts by mass or less. By setting the value below the aforementioned upper limit, the appearance of the resulting molded product tends to improve further.

[0080] In this embodiment, the content of the reinforcing filler (preferably glass fiber) in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more. Furthermore, the content of the reinforcing filler (preferably glass fiber) is more preferably 60% by mass or less, even more preferably 55% by mass or less, even more preferably 45% by mass or less, even more preferably 40% by mass or less, and even more preferably 35% by mass or less. Setting the content above the lower limit tends to further increase the mechanical strength. Furthermore, setting the content below the upper limit tends to further improve the appearance of the resulting molded product. The resin composition in this embodiment may contain only one type of reinforcing filler (preferably glass fiber) or two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0081] <Flame retardant (J)> The resin composition in this embodiment may contain a flame retardant. The inclusion of a flame retardant improves the adhesion of the molded product formed from the resin composition to other components. It is presumed that the inclusion of a flame retardant forms a flame retardant region on the surface of the molded product, increasing the arithmetic mean height (Sa) and improving adhesion. Examples of flame retardants include brominated flame retardants and phosphorus-based flame retardants, with brominated flame retardants being preferred, and brominated epoxy compounds being particularly preferred. Examples of brominated flame retardants include brominated polycarbonate resins, brominated phenoxy resins, brominated polyphenylene ether resins, brominated polystyrene resins, brominated acrylate resins, brominated epoxy compounds, and brominated imides (such as brominated phthalimides). The brominated polycarbonate resin is preferably a brominated polycarbonate obtained from brominated bisphenol A, particularly tetrabromobisphenol A. Its terminal structure may include a phenyl group, a 4-t-butylphenyl group, or a 2,4,6-tribromophenyl group, with a 2,4,6-tribromophenyl group being particularly preferred in the terminal group structure. Examples of brominated acrylate resins include polymers of pentabrombenzyl acrylate, tetrabrombenzyl acrylate, tribrombenzyl acrylate, or mixtures thereof, and among these, polymers obtained by polymerizing benzyl (meth)acrylate containing bromine atoms alone, copolymerizing two or more types, or copolymerizing with other vinyl monomers are preferred. The bromine atoms are attached to the benzene ring, and the number of attached atoms is preferably 1 to 5 per benzene ring, with 4 to 5 being particularly preferred. Examples of brominated epoxy compounds include bisphenol A type brominated epoxy compounds, such as tetrabromobisphenol A epoxy compounds. The molecular weight of the brominated epoxy compound is arbitrary and can be selected and determined as appropriate, but it is preferable that the weight-average molecular weight (Mw) is, for example, 10,000 or more, more preferably 15,000 or more, even more preferably 18,000 or more, even more preferably 20,000 or more, and particularly preferably 22,000 or more. Alternatively, it is preferable that it is, for example, 100,000, more preferably 80,000 or less, even more preferably 78,000 or less, even more preferably 75,000 or less, and particularly preferably 70,000 or less. The brominated epoxy compound preferably has an epoxy equivalent of 1000 g / eq or more, more preferably 2000 g / eq or more, even more preferably 3000 g / eq or more, and preferably 40000 g / eq or less, more preferably 35000 g / eq or less, and especially preferably 30000 g / eq or less. Examples of phosphorus-based flame retardants include (di)phosphinate metal salts such as aluminum ethylphosphinate, aluminum diethylphosphinate, aluminum ethylmethylphosphinate, and zinc diethylphosphinate; reaction products of melamine and phosphoric acid, such as melamine polyphosphate; phosphoric acid esters; and phosphazenes such as cyclic phenoxyphosphazenes, linear phenoxyphosphazenes, and crosslinked phenoxyphosphazenes. Among these, (di)phosphinate metal salts, melamine polyphosphate, and phosphazenes are preferred due to their excellent thermal stability. In addition to the above, the descriptions in paragraphs 0068 to 0075 of Japanese Patent Publication No. 2016-216534 can be given to the use of flame retardants, and these contents are incorporated herein by reference.

[0082] If the resin composition in this embodiment contains a flame retardant, the amount is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more, per 100 parts by mass of polybutylene terephthalate resin. Setting the amount above the lower limit tends to further improve the adhesion of the molded product formed from the resin composition to other components. As for the upper limit, it is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less, per 100 parts by mass of polybutylene terephthalate resin. If the resin composition in this embodiment contains a flame retardant, it may contain only one type or two or more types. If it contains two or more types, it is preferable that the total amount is within the above range.

[0083] <Drip prevention agent (K)> The resin composition in this embodiment preferably contains an anti-dripping agent (K). A fluoropolymer is preferred as the anti-dripping agent (K). Any known polymer containing fluorine can be arbitrarily selected and used as the fluoropolymer, but fluoroolefin resins are particularly preferred. Examples of fluoroolefin resins include polymers and copolymers containing a fluoroethylene structure. Specific examples include difluoroethylene resins, tetrafluoroethylene resins, and tetrafluoroethylene / hexafluoropropylene copolymer resins. Among these, tetrafluoroethylene resins are preferred. Among these fluoroethylene resins, fluoroethylene resins having fibril-forming ability are preferred. Examples of fluoroethylene resins that have fibril-forming ability include Teflon® 6J from Mitsui DuPont Fluorochemicals, Polyflon® F201L and Polyflon® F103 from Daikin Industries, Ltd.

[0084] Furthermore, examples of aqueous dispersions of fluoroethylene resins include Teflon® 30J from Mitsui DuPont Fluorochemicals, Fluon D-1 and M12 from Daikin Industries, and TF1750 from Sumitomo 3M. In addition, fluoroethylene polymers having a multilayer structure formed by polymerizing vinyl monomers can also be used as fluoropolymers. A specific example of this is Metabrane® A-3800 from Mitsubishi Rayon.

[0085] If the resin composition in this embodiment contains an anti-dripping agent (K), its content is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 1 part by mass or more, and even more preferably 1.5 parts by mass or more, per 100 parts by mass of polybutylene terephthalate resin. Setting the content above the lower limit tends to further improve the adhesion of the molded product formed from the resin composition to other components. As for the upper limit, it is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, even more preferably 3 parts by mass or less, even more preferably 2.5 parts by mass or less, and even more preferably 2 parts by mass or less, per 100 parts by mass of polybutylene terephthalate resin. The resin composition in this embodiment may contain only one type of anti-dripping agent (K), or it may contain two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0086] <Antimony trioxide (L)> The resin composition in this embodiment may contain antimony trioxide (L). Examples of antimony compounds include antimony trioxide (Sb2O3), antimony pentoxide (Sb2O5), and sodium antimonate, but in this embodiment, the inclusion of antimony trioxide is preferable in terms of improving flame retardancy and adhesion.

[0087] The antimony trioxide (L) is preferably blended such that the total mass ratio of bromine atoms derived from the brominated flame retardant (J) in the resin composition to the antimony atoms in the antimony trioxide (L) is 3% by mass or more, more preferably 4% by mass or more, even more preferably 10% by mass or more, and preferably 25% by mass or less, more preferably 22% by mass or less, and even more preferably 20% by mass or less. Setting it above the lower limit tends to exhibit sufficient flame retardancy, while setting it below the upper limit tends to improve the mechanical strength of the resulting multilayer. Furthermore, the mass ratio of bromine atoms to antimony atoms (Br / Sb) is preferably 0.3 or more, preferably 5 or less, and more preferably 4 or less. Setting it within this range tends to easily exhibit flame retardancy and is therefore preferable.

[0088] In this embodiment, it is preferable to use antimony trioxide (L) that has been pre-masterbatched, and more preferably, to blend it as a masterbatch with crystalline thermoplastic resin (A). This results in good thermal stability during melt mixing and molding, suppresses the decrease in impact resistance, and tends to reduce variations in flame retardancy and impact resistance.

[0089] The antimony(L) trioxide content in the masterbatch is preferably 20% by mass or more, and 90% by mass or less. By setting the antimony(L) content to 20% by mass or more, the proportion of antimony compounds in the flame retardant masterbatch becomes sufficient, effectively enhancing the flame retardancy. On the other hand, by setting the antimony(L) content to 90% by mass or less, the dispersibility of antimony(L) trioxide is improved, reducing concerns about the flame retardancy of the resin composition and improving workability during masterbatch production. For example, when manufacturing using an extruder, the strands become more stable and less prone to breakage. The antimony(L) trioxide content in the masterbatch is preferably 30% by mass or more, and 85% by mass or less.

[0090] In this embodiment, if the resin composition contains antimony trioxide (L), the content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 8 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of crystalline thermoplastic resin (A). Setting the content above the lower limit tends to further improve the adhesion of the molded product formed from the resin composition to other components. As for the upper limit, it is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 18 parts by mass or less, per 100 parts by mass of crystalline thermoplastic resin. The resin composition in this embodiment may contain only one type of antimony(L) trioxide, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0091] <Other ingredients> The resin composition in this embodiment may contain other components as needed, as long as they do not significantly impair the desired physical properties. Examples of other components include various resin additives. Examples of resin additives include antioxidants, UV absorbers, antistatic agents, flame retardant additives, antifogging agents, antiblocking agents, flow improvers, plasticizers, dispersants, and antibacterial agents. The resin additive may contain only one type, or two or more types in any combination and ratio. For antistatic agents, refer to paragraphs 0063 to 0067 of Japanese Patent Publication No. 2016-216534, and these contents are incorporated herein by reference.

[0092] In this embodiment, the resin composition preferably contains 40% by mass or more of (A) a crystalline thermoplastic resin, (B) an acid-modified polymer, and (C) other amorphous thermoplastic resins, in total, more preferably 50% by mass or more, and more preferably 55% by mass or more. The upper limit is preferably 90% by mass or less, and may be 85% by mass or less. In this embodiment, the resin composition preferably contains 95% by mass or more of the total of (A) crystalline thermoplastic resin, (B) acid-modified polymer, (C) other amorphous thermoplastic resin, (D) epoxy group-containing compound, (E) mold release agent, (F) impact modifier, (G) stabilizer, (H) colorant, (I) reinforcing filler, (J) flame retardant, (K) anti-dripping agent, and (L) antimony trioxide, and more preferably 98% by mass or more. The upper limit may be 100% by mass. The resin composition in this embodiment is prepared so that the total of (A) a crystalline thermoplastic resin, (B) an acid-modified polymer, and (C) another amorphous thermoplastic resin, as well as other components added as needed, amounts to 100% by mass.

[0093] <Physical properties of resin compositions> In this embodiment, the resin composition, when molded into a disc with a diameter of 100 mm and a thickness of 1.6 mm, preferably exhibits a disc warp of less than 5 mm, and more preferably less than 3 mm. While an ideal lower limit for the warp is 0 mm, a value of 0.01 mm or more is practical. Such low warp is achieved by incorporating an amorphous thermoplastic resin. The aforementioned warp is measured according to the method described in the embodiments described later.

[0094] <Method for producing resin compositions> There are no limitations on the method for producing the resin composition in this embodiment, and a wide range of known methods for producing resin compositions can be used. For example, a method may be used in which a crystalline thermoplastic resin (A), an acid-modified polymer (B), and other components that may be added as needed are pre-mixed using various mixers such as a tumbler or a Henschel mixer, and then melt-kneaded using a mixer such as a Banbury mixer, rolls, brabender, single-screw extruder, twin-screw extruder, or kneader. The melt-kneading temperature is not particularly limited, but is usually in the range of 220 to 320°C.

[0095] <Molded products> The resin composition described above (for example, pellets) is molded into a molded product by various molding methods. That is, the molded product of this embodiment is molded from the resin composition of this embodiment as described above. There are no particular restrictions on the shape of the molded product, and it can be appropriately selected according to the use and purpose of the molded product. Examples include film-shaped, rod-shaped, cylindrical, annular, circular, elliptical, polygonal, irregularly shaped, hollow, frame-shaped, box-shaped, panel-shaped, and button-shaped products. Among these, film-shaped, frame-shaped, panel-shaped, and button-shaped products are preferred, and the thickness is, for example, about 1 mm to 5 mm in the case of frame-shaped and panel-shaped products.

[0096] The method for molding the molded product is not particularly limited, and conventionally known molding methods can be used. Examples include injection molding, injection compression molding, extrusion molding, shape extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating) molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding. In particular, the resin composition in this embodiment is suitable for molded products obtained by injection molding, injection compression molding, and extrusion molding. When performing mold molding, such as injection molding, the mold temperature is preferably 40 to 130°C. If the mold temperature is low, the arithmetic mean height increases, and the adhesive strength tends to improve, but the appearance deteriorates. If the mold temperature is high, the arithmetic mean height decreases, and the appearance improves, but the adhesive strength tends to decrease. The mold temperature is preferably around 60 to 100°C, and within this range, both adhesive strength and appearance can be effectively improved. However, it goes without saying that the resin compositions in this embodiment are not limited to the molded articles obtained therefrom. [Examples]

[0097] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or other reasons, measurements can be taken using other instruments with equivalent performance.

[0098] 1. Raw materials The raw materials shown in Tables 1 and 2 below were used. [Table 1]

[0099] [Table 2]

[0100] 2. Examples 1-19, Comparative Examples 1-3 <Compound> From the components shown in Table 1 or Table 2 above, the components excluding the reinforcing filler were uniformly mixed in a tumbler mixer in the proportions (all parts by mass) shown in Tables 3-1 to 6-2. Then, using a twin-screw extruder (TEX30α, manufactured by Japan Steel Works, Ltd., L / D=42), with the reinforcing filler supplied from a side feeder, the resin composition was melt-kneaded under the conditions of a cylinder temperature of 260°C, a discharge rate of 40 kg / h, and a screw rotation speed of 200 rpm. The resulting resin composition was rapidly cooled in a water bath and pelletized using a pelletizer to obtain pellets of the resin composition.

[0101] <Method for measuring acid content> The acid content in the resin composition was calculated from the acid content (e.g., maleic anhydride) in the raw material (e.g., maleic anhydride polymer). Specifically, it was calculated by multiplying the acid-modified polymer content by the acid content in the polymer in 100 parts by mass of the resin composition including all additives.

[0102] <Tensile strength> After drying the pellets obtained above at 120°C for 5 hours, ISO multipurpose test specimens (4 mm thick) were injection molded using a Japan Steel Works injection molding machine (clamping force 85T) under the conditions of cylinder temperature 250°C and mold temperature 80°C. In accordance with ISO 527, the tensile strength (unit: MPa) was measured using the above ISO multipurpose test specimen (4 mm thick).

[0103] <Bending properties> In accordance with ISO 178, the bending strength (in MPa) and bending modulus (in MPa) were measured at a temperature of 23°C using the above ISO multipurpose test specimen (4 mm thick).

[0104] <Charpy impact strength> In accordance with ISO 179, the notched test specimens, which were prepared by notching the above ISO multipurpose test specimen (4 mm thick), were subjected to the Charpy impact strength test (unit: kJ / m²) at a temperature of 23°C. 2 ) was measured.

[0105] <Disc-shaped curvature> Using the above resin composition, a disc with a diameter of 100 mm and a thickness of 1.6 mm was molded using a side gate mold in an injection molding machine (NEX80-9E, manufactured by Nissei Plastic Industrial Co., Ltd.) under conditions of cylinder temperature of 260°C and mold temperature of 80°C. After molding, the disc was left overnight in a 23°C, 50% RH environment, and the amount of warping of the disc (in mm) was determined. The following criteria were used to evaluate the low warping properties. A: Curvature is less than 3mm B: Curvature of 3mm or more but less than 5mm C: Curvature of 5mm or more

[0106] <Arithmetic mean height (Sa)> Examples 1-6, 9-19, and Comparative Examples 1-3 were prepared in accordance with ISO 179 to produce the above ISO multipurpose test specimens (4 mm thick). Example 7 was prepared in accordance with ISO 179 except that the mold temperature during molding was changed to 40°C, and Example 8 was prepared in accordance with ISO 179 except that the mold temperature during molding was changed to 120°C. The surface of the above ISO multipurpose test specimens (4 mm thick) was observed with a 10x objective lens of a hybrid laser microscope (LASERTEC OPTELICS HYBRID), and the arithmetic mean height (Sa) was measured in accordance with ISO 25178 using the accompanying analysis software (Lasertec Microscope Solution Software LMeye7). Measurements were taken using the Fine Peak measurement algorithm to obtain an FZ image of the average surface irregularities at the center of the chuck portion of an ISO multipurpose test specimen. The measurement range was defined as the center of the bond area with the adhesive. The cutoff value λc was 0.8000 mm. The same operation was repeated 30 times at arbitrarily different locations, and the average value was calculated.

[0107] <Bonding strength and interface state with epoxy adhesives> Examples 1-6, 9-19, and Comparative Examples 1-3 were prepared in accordance with ISO 179, with two of the above ISO multipurpose test specimens (4 mm thick). Example 7 was prepared in accordance with ISO 179, except that the mold temperature during molding was changed to 40°C, and Example 8 was prepared in accordance with ISO 179, except that the mold temperature during molding was changed to 120°C. As shown in Figure 1, a fluoropolymer tape 2 (Nitto Corporation, NITOFLON adhesive tape, 0.18 x 10 x 10 mm) was attached to the chuck portion of one of the ISO multipurpose test specimens 1. Next, adhesive 3 was applied so that the application area of ​​adhesive 3 was 20 mm x 20 mm x 0.18 mm thick, and after bonding it to the other ISO multipurpose test specimen 4 (4 mm thick), it was fixed with a binder clip, and the adhesive was treated under the specified curing conditions to bond it. ISO multipurpose test specimens 1-4 were subjected to tensile testing using a Tensilon 1t machine, under tension at 5 mm / min in the direction of the arrow shown in Figure 1. Spacers were used to ensure the specimens were vertical during the tensile testing. The unit of adhesive strength is indicated in Newtons (N). Furthermore, the interface condition after bonding was checked and described as follows. If material failure occurs after testing: Base material failure If adhesive failure occurs after testing: cohesive failure If delamination occurs at the adhesive-resin interface after testing: Interfacial delamination Furthermore, a one-component, heat-curing epoxy adhesive was used.

[0108] <Adhesion strength and interface state with modified silicone adhesives> In the test of bonding strength with the epoxy adhesive described above, the adhesive was changed to a modified silicone adhesive (a one-component, room-temperature curing adhesive mainly composed of a modified silicone polymer), and all other procedures were carried out in the same manner. The unit of adhesive strength is indicated in Newtons (N). We also checked the interface condition after bonding.

[0109] <Bonding strength and interface state with urethane adhesive> In the test of bonding strength with the epoxy adhesive mentioned above, the adhesive was changed to a urethane-based adhesive, while all other procedures remained the same. The unit of adhesive strength is indicated in Newtons (N). We also checked the interface condition after bonding.

[0110] <Bonding strength and interface state with acrylic adhesives> I prepared a piece of die-cast aluminum measuring 12mm x 45mm and 1.5mm thick. Using the above resin composition, a flat plate measuring 100 mm wide x 100 mm thick and 2 mm thick was manufactured using a film gate mold in an injection molding machine (Nissei Plastic Industrial Co., Ltd. "NEX80-9E") under conditions of cylinder temperature of 260°C and mold temperature of 80°C, and then cut into 50 mm x 10 mm pieces using a processing machine. A fluoropolymer tape (Nitto NITOFLON adhesive tape, 0.18 x 10 x 10 mm) was applied to the edge of the processed flat plate. Next, acrylic adhesive was applied to an area of ​​10 mm x 10 mm x 0.18 mm thickness, and bonded to an aluminum die-cast (1.5 mm thick). After fixing with a binder clip, the adhesive was cured according to the specified conditions to ensure proper bonding. After bonding, the test specimens were subjected to a tensile test using a Tensilon 1t at a rate of 5 mm / min. Spacers were used to ensure the test specimens were vertical during the tensile test. The unit of adhesive strength is indicated in Newtons (N). We also checked the interface condition after bonding.

[0111] <Overall Adhesion Evaluation> Based on the above adhesive strength and interfacial state, the following evaluation was performed. Regarding the bonding of epoxy adhesives, cases where the base material is destroyed are designated as 'a'. Adhesion strength (N) with modified silicone adhesives: Products with an adhesive strength of 650N or higher were designated as 'a', and those with an adhesive strength of 350N or higher but less than 650N were designated as 'b'. Overall evaluation: Items with two 'a's were rated A, items with one 'a' and one 'b' were rated B, items with one 'a' and zero 'b' were rated C, and items with zero 'a's and zero 'b' were rated D.

[0112] [Table 3-1] [Table 3-2]

[0113] [Table 4-1] [Table 4-2]

[0114] [Table 5-1] [Table 5-2]

[0115] [Table 6]

[0116] As is clear from the results above, the resin compositions of the examples exhibited excellent adhesion to other components (Examples 1-19). Furthermore, the inclusion of amorphous resin effectively suppressed warping. Furthermore, the maleic anhydride-modified polymers—styrene-maleic anhydride polymer, styrene-N-phenylmaleimide-maleic anhydride polymer, and α-olefin-maleic anhydride polymer—all exhibited excellent adhesion to other materials, with the styrene-maleic anhydride polymer showing the best adhesion to other materials (Examples 1-17). In contrast, when the acid-modified polymer was not included (Comparative Example 1), the adhesion was poor (Comparative Example 2). Even when the acid-modified polymer was included, the adhesion was poor when the amount of acid in the resin composition was insufficient (Comparative Example 3). [Explanation of symbols]

[0117] 1 ISO multipurpose test specimen 2. Fluorine-based resin tape 3. Adhesive 4 ISO multipurpose test specimens

Claims

1. A resin composition comprising a crystalline thermoplastic resin (A) and an acid-modified polymer (B), The content of the crystalline thermoplastic resin (A) in the resin composition is greater than the content of the acid-modified polymer (B) in the resin composition. The acid content in the aforementioned resin composition is 0.5% by mass or more, The crystalline thermoplastic resin (A) comprises a polybutylene terephthalate resin, The acid-modified polymer (B) comprises a styrene-maleic anhydride polymer. Furthermore, it includes an amorphous thermoplastic resin (C) other than the acid-modified polymer (B), The amorphous thermoplastic resin (C) includes a styrene-based resin, Furthermore, an adhesive resin composition containing a reinforcing filler.

2. The adhesive resin composition according to claim 1, wherein the weight-average molecular weight of the acid-modified polymer (B) is 150,000 or more.

3. Furthermore, the adhesive resin composition according to claim 1 or 2 further comprises an impact modifier.

4. The adhesive resin composition according to claim 3, wherein the impact modifier comprises a core-shell elastomer.

5. A molded article formed from the adhesive resin composition described in claim 1 or 2.

6. A molded article formed from a resin composition containing a crystalline thermoplastic resin (A) and an acid-modified polymer (B), The molded product has other components that are bonded to it directly or at least via an adhesive, The content of the crystalline thermoplastic resin (A) in the resin composition is greater than the content of the acid-modified polymer (B) in the resin composition. The acid content in the aforementioned resin composition is 0.5% by mass or more, The crystalline thermoplastic resin (A) comprises a polybutylene terephthalate resin, The acid-modified polymer (B) comprises a styrene-maleic anhydride polymer. The resin composition further comprises an amorphous thermoplastic resin (C) other than the acid-modified polymer (B), The amorphous thermoplastic resin (C) includes a styrene-based resin, The resin composition further comprises a multilayer body containing glass fibers.

7. The multilayer body according to claim 6, wherein the molded product and the other component are directly bonded together in part.

8. The aforementioned multilayer body further includes an adhesive, The multilayer body according to claim 6 or 7, wherein the molded product and the other member are bonded together at least in part via an adhesive.

9. The multilayer according to claim 6 or 7, wherein the weight-average molecular weight of the acid-modified polymer (B) is 150,000 or more.

10. The multilayer according to claim 6 or 7, wherein the arithmetic mean height (Sa) of the region of the molded product that is bonded to other components is 1.0 or greater, in accordance with ISO 25178.

11. The multilayer according to claim 6 or 7, wherein the resin composition further comprises an impact modifier.

12. The multilayer according to claim 11, wherein the impact modifier comprises a core-shell elastomer.

13. The multilayer according to claim 6 or 7, wherein the resin composition further comprises a flame retardant.

14. A molded article comprising a multilayer body according to claim 6 or 7.

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