WO2011155366A1 - 接着力改善用変性ポリアルキレンテレフタレート樹脂、接着力改善用変性ポリアルキレンテレフタレート樹脂組成物、樹脂成形体、及び接合体 - Google Patents
接着力改善用変性ポリアルキレンテレフタレート樹脂、接着力改善用変性ポリアルキレンテレフタレート樹脂組成物、樹脂成形体、及び接合体 Download PDFInfo
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- WO2011155366A1 WO2011155366A1 PCT/JP2011/062478 JP2011062478W WO2011155366A1 WO 2011155366 A1 WO2011155366 A1 WO 2011155366A1 JP 2011062478 W JP2011062478 W JP 2011062478W WO 2011155366 A1 WO2011155366 A1 WO 2011155366A1
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- Prior art keywords
- resin
- terephthalate resin
- polyalkylene terephthalate
- modified
- adhesive strength
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
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Definitions
- the present invention relates to a modified polyalkylene terephthalate resin for improving adhesive strength, a resin composition containing the resin, a resin molded body obtained by molding the resin composition, and a bonded body obtained by bonding the resin molded body to another molded body.
- a resin composition containing the resin a resin molded body obtained by molding the resin composition
- a bonded body obtained by bonding the resin molded body to another molded body a modified polyalkylene terephthalate resin for improving adhesive strength
- Polyalkylene terephthalate resins have excellent mechanical strength, heat resistance, electrical properties, and moldability, and are therefore used in various fields as engineering plastics.
- polybutylene terephthalate resin has particularly excellent mechanical strength, electrical properties, other physical and chemical properties, and is excellent in processability. For this reason, polybutylene terephthalate resins are used as engineering plastics in a wide range of applications such as automobiles, electrical / electronic parts, and the like.
- an epoxy-based adhesive, a silicone-based adhesive, or the like can be used, but a silicone-based adhesive is preferably used for parts that require heat resistance, cold resistance, and the like.
- improvement in the adhesion between the resin molded body and the silicone-based adhesive has been promoted.
- a technique for improving the adhesive strength between a resin molded body containing a polybutylene terephthalate resin and a silicone-based adhesive is known. (Patent Documents 1 and 2).
- Patent Document 1 discloses a polybutylene terephthalate resin having good adhesion to a silicone-based adhesive.
- Patent Document 2 discloses a method for improving the adhesiveness of a resin molded product to a silicone-based adhesive by incorporating a specific elastomer and glass fiber in a polybutylene terephthalate resin composition.
- Patent Documents 3 and 4 disclose a technique for making it easier to weld to another member by utilizing a decrease in melting point due to a decrease in crystallinity.
- Patent Document 4 the technique which suppresses the deformation
- the present invention has been made to solve the above problems, and an object of the present invention is to provide a technique for improving the adhesiveness of a resin molded article containing a polyalkylene terephthalate resin to a silicone-based adhesive.
- the inventors of the present invention have made extensive studies to solve the above problems.
- polyalkylene terephthalate in which aromatic dicarboxylic acid excluding terephthalic acid and / or esterified product thereof is copolymerized as a modifying component, and the content of the modifying component with respect to all dicarboxylic acid components is 13 mol% or more and 35 mol% or less.
- the present inventors have found that the above problems can be solved by using a resin, and have completed the present invention. More specifically, the present invention provides the following.
- Modified polyalkylene terephthalate resin for improving power is 13 mol% or more and 35 mol% or less.
- modified polyalkylene terephthalate resin for improving adhesive strength according to (1) wherein the modified polyalkylene terephthalate resin is a modified polybutylene terephthalate resin.
- aromatic dicarboxylic acid excluding terephthalic acid and / or its esterified product is copolymerized as a modifying component, and the content of the modifying component with respect to the total dicarboxylic acid component is adjusted to 13 mol% or more and 35 mol% or less.
- the modified polyalkylene terephthalate resin for improving adhesive strength of the present invention (sometimes referred to as “the polyalkylene terephthalate resin of the present invention” in the present specification) is a modification of an aromatic dicarboxylic acid excluding terephthalic acid and / or its esterified product. It is contained as a component, and the content of the modifying component with respect to the total dicarboxylic acid component is 13 mol% or more and 35 mol% or less.
- the modified component imparts a bent structure to the polymer. When a bent structure is imparted to the polymer, the degree of crystallinity is lowered, and some physical properties such as mechanical strength may be lowered, but the adhesiveness with a silicone-based adhesive described later is greatly improved. .
- the content of the modifying component is 13 mol% or more, it is preferable because the adhesiveness of the resin molding obtained using the resin of the present invention to the silicone-based adhesive can be improved.
- the content of the modifying component is 35 mol% or less, a decrease in the physical properties of the polyalkylene terephthalate resin due to a decrease in crystallinity is suppressed, and furthermore, when the resin is molded, since the melting point difference from the unmodified polyalkylene terephthalate is small. This is also preferable when productivity is taken into consideration since the solidification of the resin is sufficient and the molding cycle is in an appropriate range.
- About the upper limit of content it can set suitably according to a use.
- the polyalkylene terephthalate resin of the present invention is a resin obtained by polycondensation of a dicarboxylic acid component and a glycol component containing an alkylene glycol or an esterified product thereof.
- the polyalkylene terephthalate resin of the present invention contains an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product (modified component) as a dicarboxylic acid component. This does not mean that terephthalic acid is included as a copolymerization component.
- a resin containing terephthalic acid as a copolymerization component and an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a copolymerization component is also included in the resin of the present invention.
- aromatic dicarboxylic acids excluding terephthalic acid and / or esterified products thereof include C 8-14 aromatics such as isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-dicarboxydiphenyl ether.
- dicarboxylic acid components can be used alone or in combination of two or more.
- aromatic dicarboxylic acid excluding terephthalic acid and / or its esterified product (modified component) it is particularly preferable to use isophthalic acid and / or an esterified product thereof.
- glycol component examples include C 2 ⁇ such as 1,4-butanediol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, and 1,3-octanediol.
- alkylene glycols such as diethylene glycol, triethylene glycol and dipropylene glycol; cycloaliphatic diols such as cyclohexanedimethanol and hydrogenated bisphenol A; aromatics such as bisphenol A and 4,4′-dihydroxybiphenyl diols, ethylene oxide 2 mol adduct of bisphenol a, propylene oxide 3 mol adduct of bisphenol a, alkylene oxide adducts of C 2-4 of bisphenol a Or ester-forming derivatives of these glycols (acetylated, etc.).
- polyoxyalkylene glycols such as diethylene glycol, triethylene glycol and dipropylene glycol
- cycloaliphatic diols such as cyclohexanedimethanol and hydrogenated bisphenol A
- aromatics such as bisphenol A and 4,4′-dihydroxybiphenyl diols, ethylene oxide 2 mol adduct of bisphenol a, prop
- modified polybutylene terephthalate resin is particularly preferable.
- Modified polybutylene terephthalate resin is a resin containing terephthalic acid, aromatic dicarboxylic acid excluding terephthalic acid and / or its esterified product (modified component) as a dicarboxylic acid component, and 1,4-butanediol as a glycol component. It is.
- the modified polybutylene terephthalate resin contains 13 mol% or more and 35 mol% or less of the modified component with respect to the total dicarboxylic acid component.
- the degree of crystallinity is lowered and the physical properties and the like tend to be lowered.
- the polybutylene terephthalate resin has very good physical properties among the polyalkylene terephthalate resins, even if the physical properties are slightly reduced due to the above-mentioned decrease in crystallinity, the mechanical strength is very excellent for the resin molded body, Electrical properties and other physical and chemical properties can be imparted.
- the high adhesiveness with a silicone adhesive agent can also be provided with respect to the resin molding obtained.
- the polyalkylene terephthalate resin of the present invention can also contain components other than the monomers described above within a range not impairing the effects of the present invention.
- the amount of terminal carboxyl groups of the polyalkylene terephthalate resin of the present invention is not particularly limited as long as the object of the present invention is not impaired.
- the amount of terminal carboxyl groups of the polyalkylene terephthalate resin used in the present invention is preferably 30 meq / kg or less, and more preferably 25 meq / kg or less.
- a polyalkylene terephthalate resin having a terminal carboxyl group content in such a range is used, it is difficult to receive a decrease in strength due to hydrolysis in a wet heat environment.
- the melt index (MI) of the polyalkylene terephthalate resin of the present invention is not particularly limited as long as the object of the present invention is not impaired.
- the melt index is preferably 5 g / min or more and 140 g / min or less. More preferably, it is 20 g / min or more and 100 g / min or less.
- the resin composition has particularly excellent moldability.
- the melt index is measured under the conditions of 235 ° C. and load of 2160 g by a method based on ASTM D-1238.
- the melt index can be adjusted by blending polyalkylene terephthalate resins having different melt indexes, other resins, and other components (additives, etc.).
- the crystallinity of the polyalkylene terephthalate resin of the present invention is not particularly limited, it is generally considered that a lower crystallinity is preferable.
- a lower crystallinity is preferable.
- the crystallinity can be adjusted by adjusting the content of the modifying component. Assuming that the value obtained by the derivation method using the following formula (I) is adopted as the crystallinity, when the crystallinity is 22% or less, the effect of improving the adhesiveness with the silicone-based adhesive is remarkable.
- ⁇ in the formula (I) is the density of the resin to be measured
- ⁇ a is the density when the resin to be measured can be regarded as 0% crystallinity
- ⁇ c is the crystallinity of the resin to be measured 100%. It is the density when it can be regarded as.
- the production method of the polyalkylene terephthalate resin of the present invention is not particularly limited, but can be suitably produced by a conventionally known method such as interfacial polycondensation using a condensation reaction or a transesterification reaction, melt polymerization, solution polymerization or the like.
- the degree of polymerization of the resin can be further increased by heat-treating the obtained resin under reduced pressure or in the presence of an inert gas to cause solid phase polymerization.
- the modified polyalkylene terephthalate resin composition for improving adhesive force of the present invention includes the modified polyalkylene terephthalate resin for improving adhesive force, and other than modified polyalkylene terephthalate.
- An adhesion improver for improving the adhesion to the silicone adhesive may be contained.
- the modified polyalkylene terephthalate resin for improving adhesive strength is the same as described above, and thus the description thereof is omitted.
- the adhesion improver is a component for improving the adhesion with a silicone adhesive other than the modified polyalkylene terephthalate.
- a silicone adhesive other than the modified polyalkylene terephthalate.
- styrenic thermoplastic elastomer polysiloxane having hydrogen atom bonded to silicon atom and trialkoxysilylalkyl group, silane or siloxane having acryloxyalkyl group and organic peroxide, epoxy group and / or ester on silicon atom
- examples thereof include compounds containing silicon such as polysiloxane having a group and a hydrogen atom directly bonded to a silicon atom.
- compounds that are conventionally known as components that improve adhesion to silicone adhesives, and compounds that have a structure that contributes to improving adhesion to silicone adhesives are also adhesion improvers. .
- the resin composition of the present invention may contain other resins within a range that does not impair the effects of the present invention, and within a range that does not impair the effects of the present invention, a nucleating agent, a colorant, an antioxidant, You may contain conventionally well-known additives, such as a stabilizer, a plasticizer, a lubricant, a mold release agent, and a flame retardant.
- the resin composition of the present invention can be easily prepared using general equipment and methods conventionally used for preparing resin compositions.
- the resin molded body of the present invention is formed by molding the resin composition of the present invention.
- the molded article of the present invention is excellent in adhesiveness with a silicone-based adhesive.
- the silicone adhesive will also be described later.
- a conventionally known method can be employed as a molding method for producing the resin molded body.
- Examples of conventionally known molding methods include injection molding methods, injection compression molding methods, gas assist injection molding methods, heat compression molding methods, extrusion molding methods, and blow molding methods.
- the bonded body of the present invention is a bonded body in which a pair of molded bodies are bonded via a silicone adhesive, and at least one of the pair of molded bodies is the resin molded body of the present invention. Since the resin molded body of the present invention is excellent in adhesiveness to the silicone adhesive, the problem of poor adhesion hardly occurs at the location where the resin molded body of the present invention and the silicone adhesive are bonded.
- Silicone adhesive is an adhesive that cures at room temperature or by heating, and conventionally known adhesives can be used.
- an addition reaction type silicone adhesive that cures by an addition reaction with a platinum catalyst is used. It is preferable to do.
- the manufacturing method of a joined body is not specifically limited, For example, it can manufacture by the following methods.
- the number of molded bodies to be joined may be two or more.
- a silicone-based adhesive is disposed on the first resin molded body.
- the arrangement method is not particularly limited, and examples thereof include brushing and potting.
- the second resin molded body is placed on the silicone-based adhesive disposed on the first resin molded body, and the first resin molded body and the second resin molded body are in close contact with each other as necessary.
- pressure is applied in the direction in which the first resin molded body and the second resin molded body overlap.
- the silicone adhesive is cured at room temperature or by heating.
- Unmodified polybutylene terephthalate resin 1 (unmodified PBT1): manufactured by Polyplastics Co., Ltd., trade name “DURANEX 400FP” (melt index (MI): 45 g / 10 min)
- Unmodified polybutylene terephthalate resin 2 (unmodified PBT2): manufactured by Polyplastics Co., Ltd., trade name “DURANEX 500FP” (melt index (MI): 20 g / 10 min)
- the melt index was measured under the conditions of 235 ° C. and load of 2160 g by a method based on ASTM D-1238.
- Modified polybutylene terephthalate resin 1 (modified PBT1): 12.5 mol% Isophthalic acid modified polybutylene terephthalate (melt index (MI): 46 g / 10 min)
- Modified polybutylene terephthalate resin 2 (modified PBT2): 15 mol% Isophthalic acid modified polybutylene terephthalate (melt index (MI): 46 g / 10 min)
- Modified polybutylene terephthalate resin 3 (modified PBT3): 17 mol% Isophthalic acid modified polybutylene terephthalate (melt index (MI): 30 g / 10 min)
- Modified polybutylene terephthalate resin 4 (modified PBT4): 30 mol% Isophthalic acid modified polybutylene terephthalate (melt index (MI): 46 g / 10 min)
- a joined body was produced in the same manner as the above joined body except that the silicone adhesive was changed to an epoxy adhesive and the curing conditions were changed to 120 ° C. ⁇ 0.5 hours.
- the joined bodies of Examples 1 to 3 and Comparative Examples 1 to 3 manufactured using an epoxy adhesive were obtained.
- ⁇ Measurement of crystallinity> As reference values, the crystallinity of each of the unmodified polybutylene terephthalate resins 1 and 2 and the modified polybutylene terephthalate resins 1 to 4 was measured. The density of each resin was measured by an underwater substitution method (based on JIS K7112).
- the silicone adhesive strength was improved when the content of the modifying component was 13 mol% or more.
- the effect of improving the adhesive strength of the joined body was confirmed when a silicone-based adhesive was used.
- the modified PBT has an adhesive strength equivalent to that of the unmodified PBT.
- the content of the modifying component increased and the lower the crystallinity, the more improved the silicone adhesive strength.
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Abstract
Description
本発明の接着力改善用変性ポリアルキレンテレフタレート樹脂(本明細書において「本発明のポリアルキレンテレフタレート樹脂」という場合がある。)は、テレフタル酸を除く芳香族ジカルボン酸及び/又はそのエステル化物を変性成分として含み、全ジカルボン酸成分に対する上記変性成分の含有量が13モル%以上35モル%以下である。上記変性成分は、折れ曲がり構造を高分子に付与する。高分子に折れ曲がり構造が付与されると、結晶化度が低下し、機械的強度等の一部の物性も低下する場合もあるが、後述するシリコーン系接着剤との接着性は大幅に向上する。
上記の通り、変性ポリブチレンテレフタレート樹脂は、全ジカルボン酸成分に対して、上記変性成分を13モル%以上35モル%以下含む。上述の通り、変性成分を含有すると結晶化度が低下し、物性等を低下させる傾向にある。しかしながら、ポリブチレンテレフタレート樹脂はポリアルキレンテレフタレート樹脂の中でも非常に優れた物性を有するため、上記結晶化度低下により物性が少し低下しても、樹脂成形体に対して非常に優れた機械的強度、電気的性質、その他物理的、化学的性質を付与することができる。また、得られる樹脂成形体に対して、シリコーン接着剤との高い接着性も付与できる。
本発明の接着力改善用変性ポリアルキレンテレフタレート樹脂組成物(以下、「本発明の樹脂組成物」という場合がある)は、上記接着力改善用変性ポリアルキレンテレフタレート樹脂を含み、変性ポリアルキレンテレフタレート以外のシリコーン系接着剤との接着性を向上させるための接着性向上剤を含有してもかまわない。接着力改善用変性ポリアルキレンテレフタレート樹脂については、上記の説明と同様であるため、説明を省略する。
接着性向上剤とは、変性ポリアルキレンテレフタレート以外のシリコーン接着剤との接着性を向上させるための成分である。例えば、スチレン系熱可塑性エラストマー、ケイ素原子に結合した水素原子とトリアルコキシシリルアルキル基を有するポリシロキサン、アクリロキシアルキル基を有するシランまたはシロキサンと有機過酸化物、ケイ素原子にエポキシ基及び/又はエステル基とケイ素原子に直接結合した水素原子とを有するポリシロキサン等のケイ素を含む化合物が挙げられる。また、これらの化合物以外に、シリコーン系接着剤との接着性を向上させる成分として従来公知である化合物、シリコーン系接着剤との接着性向上に寄与する構造を有する化合物も接着性向上剤である。
本発明の樹脂組成物には、本発明の効果を害さない範囲でその他の樹脂を含有してもよく、また、本発明の効果を害さない範囲で、核剤、着色剤、酸化防止剤、安定剤、可塑剤、滑剤、離型剤及び難燃剤等の従来公知の添加剤を含有してもよい。
上記本発明の樹脂組成物は、従来から樹脂組成物の調製に用いられる一般的な設備、方法を用いて容易に調製することができる。
本発明の樹脂成形体とは、上記本発明の樹脂組成物を成形してなる。本発明の成形体は後述するとおり、シリコーン系接着剤との接着性に優れる。シリコーン接着剤についても後述する。
本発明の接合体とは、一対の成形体がシリコーン接着剤を介して接合した接合体であり、上記一対の成形体の少なくとも一方が本発明の樹脂成形体である。本発明の樹脂成形体は、シリコーン系接着剤との接着性に優れるため、本発明の樹脂成形体とシリコーン系接着剤とが接着する箇所は、接着不良の問題がほとんど生じない。
ここでは、第一の樹脂成形体と第二の樹脂成形体とを接合する場合について説明する。接合される成形体の数は2以上であってもよい。
先ず、第一の樹脂成形体にシリコーン系接着剤を配置する。配置方法は特に限定されず、例えば、刷毛塗り、ポッティング等の方法が挙げられる。次いで、第一の樹脂成形体上に配置されたシリコーン系接着剤上に第二の樹脂成形体を載せ、必要に応じて、第一の樹脂成形体と第二の樹脂成形体とが密着するように、第一の樹脂成形体と第二の樹脂成形体が重なる方向に圧力を加える。最後に、室温又は加熱によりシリコーン系接着剤を硬化させる。
未変性ポリブチレンテレフタレート樹脂1(未変性PBT1):ポリプラスチックス社製、商品名「ジュラネックス400FP」(メルトインデックス(MI):45g/10min)
未変性ポリブチレンテレフタレート樹脂2(未変性PBT2):ポリプラスチックス社製、商品名「ジュラネックス500FP」(メルトインデックス(MI):20g/10min)
なお、メルトインデックスは、ASTM D-1238に準拠した方法で、235℃、荷重2160gの条件で測定した。
変性ポリブチレンテレフタレート樹脂2(変性PBT2):15モル% イソフタル酸変性ポリブチレンテレフタレート(メルトインデックス(MI):46g/10min)
変性ポリブチレンテレフタレート樹脂3(変性PBT3):17モル% イソフタル酸変性ポリブチレンテレフタレート(メルトインデックス(MI):30g/10min)
変性ポリブチレンテレフタレート樹脂4(変性PBT4):30モル% イソフタル酸変性ポリブチレンテレフタレート(メルトインデックス(MI):46g/10min)
シリコーン系接着剤:東レダウコーニングシリコーン社製、商品名「SE1714」
エポキシ系接着剤:ナガセケムテックス社製、商品名「XNR3503」
未変性ポリブチレンテレフタレート樹脂1、2及び変性ポリブチレンテレフタレート樹脂1~4のそれぞれを射出成形機(ファナック社製S2000i 100B)に投入し、後述する接着強度の測定に使用する樹脂試験片(ISO3167に準拠した多目的試験片)を作製した。実施例1~3の樹脂成形体、比較例1~3の樹脂成形体が得られた。
ISO3167に準拠した多目的試験片の中央部を切断し、一方の樹脂試験片に7mm×7mmの穴を開けた日東電工株式会社製ニトフロン粘着テープ(厚み0.18mm)を貼り付け、穴の部分にシリコーン系接着剤を塗布した。塗布後、他方の樹脂試験片を重ね合わせ、クリップで固定し、120℃×1時間の条件で接着を行った。シリコーン系接着剤を用いて作製した実施例1~3接合体及び比較例1~3の接合体が得られた。
接合体を23℃、50%RHの環境に24時間以上放置し、オリエンテック製万能試験機テンシロンRTC-1325PLを用いて押し剥がし試験速度5mm/minの条件で接着した他方の樹脂試験片を押し剥がし、押し剥がし強度の最高値を測定した。測定結果は表1に示した。
<結晶化度の測定>
参考値として、未変性ポリブチレンテレフタレート樹脂1、2及び変性ポリブチレンテレフタレート樹脂1~4の各樹脂の結晶化度を測定した。各樹脂の密度は水中置換法(JIS K7112に準拠)で測定した。上記数式(I)に従い、飽和ポリエステル樹脂ハンドブック(日刊工業新聞社)より、ポリブチレンテレフタレートの結晶密度ρc=1.40、非晶密度ρa=1.28として、結晶化度を算出した。
実施例の結果から明らかなように、上記接合体の接着強度が向上する効果は、シリコーン系接着剤を使用する場合に確認された。エポキシ系接着剤を使用する場合においては、変性PBTでも、未変性PBTと同等の接着強度であることが確認された。
実施例の結果から明らかなように、変性成分の含有量が多くなり、結晶化度の低い樹脂ほど、シリコーン接着強度が向上することが確認された。
Claims (5)
- テレフタル酸を除く芳香族ジカルボン酸、及び/又はそのエステル化物を、変性成分として共重合させ、
全ジカルボン酸成分に対する前記変性成分の含有量が13モル%以上35モル%以下である接着力改善用変性ポリアルキレンテレフタレート樹脂。 - 前記変性ポリアルキレンテレフタレート樹脂が変性ポリブチレンテレフタレート樹脂である請求項1記載の接着力改善用変性ポリアルキレンテレフタレート樹脂。
- 前記芳香族ジカルボン酸及び/又はそのエステル化物が、イソフタル酸及び/又はそのエステル化物である請求項1又は2に記載の接着力改善用変性ポリアルキレンテレフタレート樹脂。
- 請求項1から3のいずれかに記載の接着力改善用変性ポリアルキレンテレフタレート樹脂組成物を成形してなる樹脂成形体。
- 一対の成形体がシリコーン接着剤を介して接合した接合体であって、
前記一対の成形体の少なくとも一方が請求項4に記載の樹脂成形体である接合体。
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CN201180036275.5A CN103025790B (zh) | 2010-06-10 | 2011-05-31 | 粘接力改善用改性聚对苯二甲酸烷二醇酯树脂、粘接力改善用改性聚对苯二甲酸烷二醇酯树脂组合物、树脂成形体、接合体 |
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MY160890A (en) | 2017-03-31 |
US20130177774A1 (en) | 2013-07-11 |
JPWO2011155366A1 (ja) | 2013-08-01 |
CN103025790A (zh) | 2013-04-03 |
JP5744018B2 (ja) | 2015-07-01 |
US11124602B2 (en) | 2021-09-21 |
CN103025790B (zh) | 2014-12-03 |
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