WO2011155367A1 - Resin composition for improving adhesive strength, resin molded article, bonded article, and agent for improving adhesive strength - Google Patents
Resin composition for improving adhesive strength, resin molded article, bonded article, and agent for improving adhesive strength Download PDFInfo
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- WO2011155367A1 WO2011155367A1 PCT/JP2011/062479 JP2011062479W WO2011155367A1 WO 2011155367 A1 WO2011155367 A1 WO 2011155367A1 JP 2011062479 W JP2011062479 W JP 2011062479W WO 2011155367 A1 WO2011155367 A1 WO 2011155367A1
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- resin
- terephthalate resin
- polyalkylene terephthalate
- modified
- adhesive
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to an adhesive force improving resin composition, a resin molded body obtained by molding the resin composition, a bonded body obtained by bonding the resin molded body to another molded body, and an adhesive strength improving agent.
- 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 easy 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 present inventors include a modified polyalkylene terephthalate resin (A) obtained by copolymerizing an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modifying component, and an unmodified polyalkylene terephthalate resin (B). It has been found that the above problems can be solved by using the mixture with the content of the modifying component adjusted to a specific range, and the present invention has been completed. More specifically, the present invention provides the following.
- the modified polyalkylene terephthalate resin (A) is a modified polybutylene terephthalate resin
- the unmodified polyalkylene terephthalate resin (B) is an unmodified polybutylene terephthalate resin. Resin composition.
- a bonded body in which a pair of molded bodies are bonded via a silicone-based adhesive, and at least one of the pair of molded articles is a resin molded body according to (4).
- An adhesive strength improver that is added to the raw material of the resin molded body in order to improve the adhesive force between the resin molded body and the silicone-based adhesive, and an aromatic dicarboxylic acid excluding terephthalic acid, and / or its Adhesion improvement wherein the modified polyalkylene terephthalate resin obtained by copolymerizing the esterified product as a modifying component is a main component, and the modification amount of the modifying component with respect to all dicarboxylic acid components is more than 12.5 mol% and not more than 35 mol%. Agent.
- A modified polyalkylene terephthalate resin
- B unmodified polyalkylene terephthalate resin
- an adhesive strength improving agent an adhesive strength improving resin composition
- a resin molded body a resin molded body
- a bonded body a resin molded body
- the adhesive force improver of the present invention is mainly composed of a modified polyalkylene terephthalate resin obtained by copolymerizing an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modifying component.
- the amount of modification exceeds 12.5 mol% and is 35 mol% or less.
- Modified polyalkylene terephthalate resin (A) contains an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a copolymer component (hereinafter, this copolymer component may be referred to as “modified component”). Further, the modification amount of the modifying component is more than 12.5 mol% and 35 mol% or less. The modified amount of the modified component refers to the content (mol%) of the repeating unit derived from the modified component in all the dicarboxylic acid components of the modified polyalkylene terephthalate resin.
- modification amount of the modifying component is 12.5 mol% or less, the effect of improving the adhesion of the resin molded body obtained using the resin composition of the present invention to the silicone-based adhesive is insufficient. If the amount of modification exceeds 35 mol%, the difference in melting point from the unmodified polyalkylene terephthalate (B) becomes large, so the component (B) is first melted during melt kneading or melt processing. ) Component and (B) component may not be uniformly melt-kneaded. About the upper limit of content, it can set suitably according to a use.
- the modified polyalkylene terephthalate resin is a resin obtained by polycondensation of a dicarboxylic acid component and a glycol component containing alkylene glycol or an esterified product thereof.
- the modified polyalkylene terephthalate resin contains an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modified component. This does not mean that terephthalic acid is included as a copolymerization component. That is, a resin containing terephthalic acid as a copolymerization component and an aromatic dicarboxylic acid excluding terephthalic acid and / or its esterified product as a copolymerization component can also be used in 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
- the modified polyalkylene terephthalate resin is particularly preferably a modified polybutylene terephthalate resin.
- 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 the modified component in excess of 12.5 mol% and 35 mol% or less with respect to the total dicarboxylic acid component.
- the modified polybutylene terephthalate resin has very good physical properties among the modified polyalkylene terephthalate resins, so it gives the molded resin a very good mechanical strength, electrical properties, and other physical and chemical properties. can do. Moreover, the high adhesiveness with a silicone type adhesive agent can also be provided with respect to the resin molding obtained.
- the modified polyalkylene terephthalate resin can also contain monomer components other than the above-described monomers within a range not impairing the effects of the present invention.
- the amount of terminal carboxyl groups of the modified polyalkylene terephthalate resin is not particularly limited as long as the object of the present invention is not impaired.
- the terminal carboxyl group amount of the modified polyalkylene terephthalate resin is preferably 30 meq / kg or less, and more preferably 25 meq / kg or less. In the case of using a modified polyalkylene terephthalate resin having a terminal carboxyl group amount in such a range, it is difficult to receive a decrease in strength due to hydrolysis in a humid 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 production method of the modified polyalkylene terephthalate resin is not particularly limited, it can be suitably produced by a conventionally known method such as interfacial polycondensation using a condensation reaction or a transesterification reaction, melt polymerization, or solution polymerization.
- 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 adhesive strength improver of the present invention may contain other components such as other resins and conventionally known additives as long as the effects of the present invention are not impaired.
- the resin composition for improving adhesive force of the present invention comprises a modified polyalkylene terephthalate resin (A) obtained by copolymerizing an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modifying component, and an unmodified polyalkylene terephthalate.
- Resin (B) In the modified polyalkylene terephthalate resin (A), the modification amount of the modification component is more than 12.5 mol% and 35 mol% or less. That is, the adhesive force improving resin composition of the present invention is a resin composition containing the adhesive force improving agent of the present invention. Moreover, the resin composition of this invention is 8 mol% or more of the total modification amount represented by following formula (I).
- the adhesiveness of the resin molded product to the silicone-based adhesive can be improved. While improving, the fall of physical properties, such as mechanical strength resulting from the fall of crystallinity, can be suppressed.
- Modified polyalkylene terephthalate resin (A) The modified polyalkylene terephthalate resin (A) is the same as described above.
- the effect of improving the adhesiveness with the silicone-based adhesive is easily obtained when the modified polybutylene terephthalate resin (A) having a large amount of modification of the modifying component is used.
- the modification amount of the modifying component in the modified polyalkylene terephthalate resin is preferably 15 mol% or more.
- the unmodified polyalkylene terephthalate resin (B) is a resin obtained by polycondensation of terephthalic acid and a glycol component containing alkylene glycol or an esterified product thereof.
- the content of the unmodified polyalkylene terephthalate resin (B) in the resin composition of the present invention is not particularly limited, and as described above, the content is such that the total modification amount is 8 mol% or more according to the formula (I). Can be adjusted.
- the resin composition of the present invention contains the modified polyalkylene terephthalate resin (A).
- the modified polyalkylene terephthalate resin contains an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product (modified component) as a copolymer component.
- These modifying components impart a bent structure to the polymer. If the polymer has a bent structure, the crystallinity of the resin generally decreases. When the crystallinity of the resin is lowered, physical properties such as mechanical strength of the resin molded body may be lowered.
- the resin composition of the present invention contains a modified polyalkylene terephthalate resin (A) and an unmodified polyalkylene terephthalate resin (B). If the unmodified polyalkylene terephthalate resin (B) is contained, even if the modified polyalkylene terephthalate resin (A) is included, a significant decrease in crystallinity as a resin composition can be avoided, and Decrease in physical properties can be suppressed. If the above-mentioned mixing suppresses the decrease in crystallinity within the above-mentioned preferable content range, the decrease in crystallinity can be sufficiently suppressed.
- ⁇ Crystal density of sample
- ⁇ c Crystal density of polyalkylene terephthalate
- the modification amount of the modification component of the modified polyalkylene terephthalate resin (A) increases (for example, the modification amount is 20 mol% or more), it becomes difficult to mold a resin molded body made of the modified polyalkylene terephthalate resin (A).
- the unmodified polyalkylene terephthalate resin (B) in combination, it can be easily molded even if the modification amount of the modifying component of the modified polyalkylene terephthalate resin (A) is large.
- the effect of improving the moldability is exhibited even when the content of the modified polyalkylene terephthalate resin (A) is very large (for example, 50% by mass or more and 90% by mass or less).
- 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 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): isophthalic acid modified polybutylene terephthalate having a modified amount of 12.5 mol% (melt index (MI): 46 g / 10 min)
- Modified polybutylene terephthalate resin 2 (modified PBT2): isophthalic acid modified polybutylene terephthalate having a modification amount of 15 mol% (melt index (MI): 46 g / 10 min)
- Modified polybutylene terephthalate resin 3 (modified PBT3): isophthalic acid modified polybutylene terephthalate having a modification amount of 17 mol% (melt index (MI): 30 g / 10 min)
- Modified polybutylene terephthalate resin 4 (modified PBT4): isophthalic acid-modified polybutylene terephthalate having a modification amount of 30 mol% (melt index (MI): 46 g / 10 min)
- ⁇ Measurement of adhesive strength The bonded body is left in an environment of 23 ° C. and 50% RH for 24 hours or more, and the other resin test piece is peeled off at a peeling test speed of 5 mm / min using a universal testing machine, and the maximum peel strength is obtained. Was measured. The measurement results are shown in Tables 1 and 2.
Abstract
Disclosed is a technique for improving the adhesiveness of a resin molded article comprising a polyalkylene terephthalate resin to a silicone-based adhesive. A mixture of (A) a modified polyalkylene terephthalate resin obtained by copolymerizing an aromatic dicarboxylic acid excluding terephthalic acid and/or an esterified product thereof as a modifying component and (B) an unmodified polyalkylene terephthalate resin, in which the content of the modifying component is adjusted in a specific range, is used. It is preferred that the modified polyalkylene terephthalate resin is a modified polybutylene terephthalate resin, and the aromatic dicarboxylic acid and/or an esterified product thereof is isophthalic acid and/or an esterified product thereof.
Description
本発明は、接着力改善用樹脂組成物、当該樹脂組成物を成形してなる樹脂成形体、当該樹脂成形体を他の成形体と接合した接合体、接着力改善剤に関する。
The present invention relates to an adhesive force improving resin composition, a resin molded body obtained by molding the resin composition, a bonded body obtained by bonding the resin molded body to another molded body, and an adhesive strength improving agent.
ポリアルキレンテレフタレート樹脂は、優れた機械的強度、耐熱性、電気的特性、成形性を有するため、エンジニアリングプラスチックとして様々な分野に利用されている。
Polyalkylene terephthalate resins have excellent mechanical strength, heat resistance, electrical properties, and moldability, and are therefore used in various fields as engineering plastics.
ポリアルキレンテレフタレート樹脂の中でも、ポリブチレンテレフタレート樹脂は、特に優れた機械的強度、電気的性質、その他物理的、化学的性質を有し、且つ加工性にも優れる。このため、ポリブチレンテレフタレート樹脂は、エンジニアリングプラスチックとして、自動車、電気・電子部品等の広範な用途に使用されている。
Among polyalkylene terephthalate resins, 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.
用途によっては、複数の樹脂成形体を接合する必要がある。樹脂成形体を接合する方法としては、接着剤による接合、二重成形、熱板溶着、振動溶着、レーザー溶着等様々な接合方法が知られている。接合方法の選択は、用途、樹脂成形体の形状等を考慮して行われ、用途によって好適な接合方法は異なる。また、他樹脂や金属との接合では溶着加工が困難なため、接着やネジ止め、かしめといった手法をとることが一般的である。
Depending on the application, it is necessary to join multiple resin moldings. As a method for joining resin moldings, various joining methods such as joining with an adhesive, double molding, hot plate welding, vibration welding, and laser welding are known. The selection of the joining method is performed in consideration of the use, the shape of the resin molded body, and the like, and a suitable joining method varies depending on the use. Further, since welding is difficult in joining with other resins or metals, it is common to adopt a technique such as bonding, screwing, or caulking.
例えば、水分やダスト、外部衝撃等からのダメージを軽減する目的で使用される、電子部品が搭載された基板を収容するケース材や、センサープローブやコネクター端子等が配置されるインサート成形品等の用途においては、接着剤による接合やポッティングによる保護が最も一般的である。
For example, case materials that contain substrates with electronic components used for the purpose of reducing damage from moisture, dust, external impact, etc., insert molded products where sensor probes, connector terminals, etc. are placed In applications, bonding by adhesive or protection by potting is the most common.
接着剤としては、エポキシ系接着剤、シリコーン系接着剤等を使用できるが、耐熱性、耐寒性等が要求される部品には、シリコーン系接着剤が好ましく使用される。また、樹脂成形体とシリコーン系接着剤との接着性の改良が進められており、例えば、ポリブチレンテレフタレート樹脂を含む樹脂成形体とシリコーン系接着剤との接着強度を改善する技術が知られている（特許文献１、２）。
As the adhesive, 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. In addition, improvement in the adhesion between the resin molded body and the silicone-based adhesive has been promoted. For example, 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).
例えば、特許文献１には、シリコーン系接着剤との接着性が良好なポリブチレンテレフタレート樹脂が開示されている。また、特許文献２には、特定のエラストマーと、ガラス繊維とをポリブチレンテレフタレート樹脂組成物に含有させて、樹脂成形体のシリコーン系接着剤との接着性を改善する方法が開示されている。
For example, 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.
近年、樹脂成形体は、従来よりもさらに過酷な環境に曝される用途への適用が検討されている。さらに過酷な環境に曝される場合、樹脂成形体とシリコーン系接着剤との接着性もさらに向上させる必要がある。
In recent years, application of resin moldings to applications that are exposed to harsher environments than before has been studied. Further, when exposed to a harsh environment, it is necessary to further improve the adhesion between the resin molded body and the silicone-based adhesive.
ところで、イソフタル酸成分等のモノマーを共重合成分として含む変性ポリブチレンテレフタレート樹脂が知られている（特許文献３、４）。特許文献３では、結晶化度が低下することによる融点の低下を利用して、他部材へ溶着させやすくする技術を開示している。特許文献４では、結晶化度の低下による成形収縮時の変形を抑制する技術を利用している。
By the way, a modified polybutylene terephthalate resin containing a monomer such as an isophthalic acid component as a copolymerization component is known (Patent Documents 3 and 4). Patent Document 3 discloses a technique for making it easy to weld to another member by utilizing a decrease in melting point due to a decrease in crystallinity. In patent document 4, the technique which suppresses the deformation | transformation at the time of shaping | molding shrinkage | contraction by the fall of a crystallinity degree is utilized.
本発明は、以上の課題を解決するためになされたものであり、その目的は、ポリアルキレンテレフタレート樹脂を含む樹脂成形体のシリコーン系接着剤に対する接着性を向上させる技術を提供することにある。
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.
本発明者らは、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、変性成分として共重合させた変性ポリアルキレンテレフタレート樹脂（Ａ）と、未変性ポリアルキレンテレフタレート樹脂（Ｂ）との混合物を、変性成分の含有量を特定の範囲に調整して使用することで、上記課題を解決できることを見出し、本発明を完成するに至った。より具体的には、本発明は以下のものを提供する。
The present inventors include a modified polyalkylene terephthalate resin (A) obtained by copolymerizing an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modifying component, and an unmodified polyalkylene terephthalate resin (B). It has been found that the above problems can be solved by using the mixture with the content of the modifying component adjusted to a specific range, and the present invention has been completed. More specifically, the present invention provides the following.
（１） 樹脂成形体とシリコーン系接着剤との接着力を改善するための、前記樹脂成形体の原料となる接着力改善用樹脂組成物であって、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た変性ポリアルキレンテレフタレート樹脂（Ａ）と、未変性ポリアルキレンテレフタレート樹脂（Ｂ）とを含み、（Ａ）において全ジカルボン酸成分に対する前記変性成分の変性量が１２．５モル％を超えて３５モル％以下であり、下記式（Ｉ）で表される総変性量が８モル％以上である接着力改善用樹脂組成物。
(1) A resin composition for improving adhesive strength as a raw material of the resin molded body for improving the adhesive strength between the resin molded body and the silicone-based adhesive, the aromatic dicarboxylic acid excluding terephthalic acid, and And / or a modified polyalkylene terephthalate resin (A) obtained by copolymerizing the esterified product as a modifying component and an unmodified polyalkylene terephthalate resin (B). A resin composition for improving adhesive strength, wherein the modification amount exceeds 12.5 mol% and is 35 mol% or less, and the total modification amount represented by the following formula (I) is 8 mol% or more.
（２） 前記変性ポリアルキレンテレフタレート樹脂（Ａ）が変性ポリブチレンテレフタレート樹脂であり、前記未変性ポリアルキレンテレフタレート樹脂（Ｂ）が未変性ポリブチレンテレフタレート樹脂である（１）に記載の接着力改善用樹脂組成物。
(2) The modified polyalkylene terephthalate resin (A) is a modified polybutylene terephthalate resin, and the unmodified polyalkylene terephthalate resin (B) is an unmodified polybutylene terephthalate resin. Resin composition.
（３） 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（１）又は（２）に記載の接着力改善用樹脂組成物。
(3) The resin composition for improving adhesive force according to (1) or (2), wherein the aromatic dicarboxylic acid and / or esterified product thereof is isophthalic acid and / or esterified product thereof.
（４） （１）から（３）のいずれかに記載の接着力改善用樹脂組成物を成形してなる樹脂成形体。
(4) A resin molded body obtained by molding the resin composition for improving adhesive strength according to any one of (1) to (3).
（５） 一対の成形体がシリコーン系接着剤を介して接合した接合体であって、前記一対の成形品の少なくとも一方が（４）に記載の樹脂成形体である接合体。
(5) A bonded body in which a pair of molded bodies are bonded via a silicone-based adhesive, and at least one of the pair of molded articles is a resin molded body according to (4).
（６） 樹脂成形体とシリコーン系接着剤との接着力を改善するために前記樹脂成形体の原料に添加する接着力改善剤であって、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た変性ポリアルキレンテレフタレート樹脂を主成分とし、全ジカルボン酸成分に対する前記変性成分の変性量が１２．５モル％を超えて３５モル％以下である接着力改善剤。
(6) An adhesive strength improver that is added to the raw material of the resin molded body in order to improve the adhesive force between the resin molded body and the silicone-based adhesive, and an aromatic dicarboxylic acid excluding terephthalic acid, and / or its Adhesion improvement wherein the modified polyalkylene terephthalate resin obtained by copolymerizing the esterified product as a modifying component is a main component, and the modification amount of the modifying component with respect to all dicarboxylic acid components is more than 12.5 mol% and not more than 35 mol%. Agent.
（７） 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（６）に記載の接着力改善剤。
(7) The adhesive force improver according to (6), wherein the aromatic dicarboxylic acid and / or esterified product thereof is isophthalic acid and / or an esterified product thereof.
本発明によれば、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た変性ポリアルキレンテレフタレート樹脂（Ａ）と、未変性ポリアルキレンテレフタレート樹脂（Ｂ）との混合物を、（Ａ）成分の変性成分の変性量及び総変性量を特定の範囲に調整して使用するため、樹脂成形体とシリコーン系接着剤との接着性を大きく改善できる。
According to the present invention, a mixture of a modified polyalkylene terephthalate resin (A) obtained by copolymerizing an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modifying component, and an unmodified polyalkylene terephthalate resin (B). Is used by adjusting the modification amount and the total modification amount of the modifying component of the component (A) within a specific range, and thus the adhesion between the resin molded product and the silicone-based adhesive can be greatly improved.
以下、本発明の実施形態について詳細に説明する。なお、本発明は以下の実施形態に限定されるものではない。
Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment.
以下、接着力改善剤、接着力改善用樹脂組成物、樹脂成形体、接合体の順で本発明について説明する。
Hereinafter, the present invention will be described in the order of an adhesive strength improving agent, an adhesive strength improving resin composition, a resin molded body, and a bonded body.
＜接着力改善剤＞
本発明の接着力改善剤は、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共重合させた変性ポリアルキレンテレフタレート樹脂を主成分とし、全ジカルボン酸成分に対する上記変性成分の変性量が１２．５モル％を超えて３５モル％以下である。樹脂組成物中に本発明の接着力改善剤が含まれると、その樹脂組成物を成形してなる樹脂成形体は、シリコーン系接着剤との接着性が高い。以下、主成分の変性ポリアルキレンテレフタレート樹脂について説明する。 <Adhesive strength improver>
The adhesive force improver of the present invention is mainly composed of a modified polyalkylene terephthalate resin obtained by copolymerizing an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modifying component. The amount of modification exceeds 12.5 mol% and is 35 mol% or less. When the adhesive strength improver of the present invention is contained in the resin composition, the resin molded body formed by molding the resin composition has high adhesiveness with the silicone-based adhesive. The main component modified polyalkylene terephthalate resin will be described below.
本発明の接着力改善剤は、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共重合させた変性ポリアルキレンテレフタレート樹脂を主成分とし、全ジカルボン酸成分に対する上記変性成分の変性量が１２．５モル％を超えて３５モル％以下である。樹脂組成物中に本発明の接着力改善剤が含まれると、その樹脂組成物を成形してなる樹脂成形体は、シリコーン系接着剤との接着性が高い。以下、主成分の変性ポリアルキレンテレフタレート樹脂について説明する。 <Adhesive strength improver>
The adhesive force improver of the present invention is mainly composed of a modified polyalkylene terephthalate resin obtained by copolymerizing an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modifying component. The amount of modification exceeds 12.5 mol% and is 35 mol% or less. When the adhesive strength improver of the present invention is contained in the resin composition, the resin molded body formed by molding the resin composition has high adhesiveness with the silicone-based adhesive. The main component modified polyalkylene terephthalate resin will be described below.
［変性ポリアルキレンテレフタレート樹脂（Ａ）］
変性ポリアルキレンテレフタレート樹脂は、共重合成分として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含む（以下、この共重合成分を「変性成分」という場合がある）。また、変性成分の変性量が１２．５モル％を超えて３５モル％以下である。変性成分の変性量とは、変性ポリアルキレンテレフタレート樹脂の全ジカルボン酸成分中の変性成分に由来する繰り返し単位の含有量（モル％）を指す。 [Modified polyalkylene terephthalate resin (A)]
The modified polyalkylene terephthalate resin contains an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a copolymer component (hereinafter, this copolymer component may be referred to as “modified component”). Further, the modification amount of the modifying component is more than 12.5 mol% and 35 mol% or less. The modified amount of the modified component refers to the content (mol%) of the repeating unit derived from the modified component in all the dicarboxylic acid components of the modified polyalkylene terephthalate resin.
変性ポリアルキレンテレフタレート樹脂は、共重合成分として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含む（以下、この共重合成分を「変性成分」という場合がある）。また、変性成分の変性量が１２．５モル％を超えて３５モル％以下である。変性成分の変性量とは、変性ポリアルキレンテレフタレート樹脂の全ジカルボン酸成分中の変性成分に由来する繰り返し単位の含有量（モル％）を指す。 [Modified polyalkylene terephthalate resin (A)]
The modified polyalkylene terephthalate resin contains an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a copolymer component (hereinafter, this copolymer component may be referred to as “modified component”). Further, the modification amount of the modifying component is more than 12.5 mol% and 35 mol% or less. The modified amount of the modified component refers to the content (mol%) of the repeating unit derived from the modified component in all the dicarboxylic acid components of the modified polyalkylene terephthalate resin.
上記変性成分の変性量が１２．５モル％以下であれば、本発明の樹脂組成物を用いて得られる樹脂成形体のシリコーン系接着剤に対する接着性向上効果が不十分である。変性量が３５モル％を超えると、未変性ポリアルキレンテレフタレート（Ｂ）との融点差が大きくなってしまうため、溶融混練時や溶融加工時に（Ｂ）成分が先に溶融してしまい、（Ａ）成分と（Ｂ）成分の溶融混練が均一に行われない場合もある。含有量の上限については用途に応じて適宜設定することができる。
If the modification amount of the modifying component is 12.5 mol% or less, the effect of improving the adhesion of the resin molded body obtained using the resin composition of the present invention to the silicone-based adhesive is insufficient. If the amount of modification exceeds 35 mol%, the difference in melting point from the unmodified polyalkylene terephthalate (B) becomes large, so the component (B) is first melted during melt kneading or melt processing. ) Component and (B) component may not be uniformly melt-kneaded. About the upper limit of content, it can set suitably according to a use.
変性ポリアルキレンテレフタレート樹脂は、ジカルボン酸成分と、アルキレングリコール又はそのエステル化物を含むグリコール成分とを重縮合して得られる樹脂である。変性ポリアルキレンテレフタレート樹脂は、ジカルボン酸成分として、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む。これは、テレフタル酸を共重合成分として含むことを排除する意味ではない。即ち、テレフタル酸を共重合成分として含み、且つ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共重合成分として含む樹脂も本発明に使用できる。
The modified polyalkylene terephthalate resin is a resin obtained by polycondensation of a dicarboxylic acid component and a glycol component containing alkylene glycol or an esterified product thereof. The modified polyalkylene terephthalate resin contains an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modified component. This does not mean that terephthalic acid is included as a copolymerization component. That is, a resin containing terephthalic acid as a copolymerization component and an aromatic dicarboxylic acid excluding terephthalic acid and / or its esterified product as a copolymerization component can also be used in the present invention.
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としては、例えば、イソフタル酸、フタル酸、２，６－ナフタレンジカルボン酸、４，４’－ジカルボキシジフェニルエーテル等のＣ８－１４の芳香族ジカルボン酸；コハク酸、アジピン酸、アゼライン酸、セバシン酸等のＣ４－１６のアルカンジカルボン酸；シクロヘキサンジカルボン酸等のＣ５－１０のシクロアルカンジカルボン酸；これらのジカルボン酸成分のエステル形成性誘導体（Ｃ１－６のアルキルエステル誘導体や酸ハロゲン化物等）が挙げられる。これらのジカルボン酸成分は、単独で又は２種以上を組み合わせて使用できる。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（変性成分）としては、イソフタル酸及び／又はそのエステル化物の使用が特に好ましい。
Examples of 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 acids; C 4-16 alkanedicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid; C 5-10 cycloalkanedicarboxylic acids such as cyclohexanedicarboxylic acid; ester-forming derivatives of these dicarboxylic acid components (C 1-6 alkyl ester derivatives, acid halides, etc.). These dicarboxylic acid components can be used alone or in combination of two or more. As the 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.
グリコール成分としては、例えば、１，４－ブタンジオール、エチレングリコール、プロピレングリコール、トリメチレングリコール、１，３－ブチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、１，３－オクタンジオール等のＣ２－１０のアルキレングリコール；ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール等のポリオキシアルキレングリコール；シクロヘキサンジメタノール、水素化ビスフェノールＡ等の脂環式ジオール；ビスフェノールＡ、４，４’－ジヒドロキシビフェニル等の芳香族ジオール；ビスフェノールＡのエチレンオキサイド２モル付加体、ビスフェノールＡのプロピレンオキサイド３モル付加体等の、ビスフェノールＡのＣ２－４のアルキレンオキサイド付加体；又はこれらのグリコールのエステル形成性誘導体（アセチル化物等）が挙げられる。これらのグリコール成分は、単独で又は２種以上を組み合わせて使用できる。
Examples of the glycol component 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. 10 alkylene glycols; 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, 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.). These glycol components can be used alone or in combination of two or more.
上記の通り、様々なジカルボン酸成分、グリコール成分を使用することができるが、変性ポリアルキレンテレフタレート樹脂は、変性ポリブチレンテレフタレート樹脂であることが特に好ましい。変性ポリブチレンテレフタレート樹脂とは、ジカルボン酸成分として、テレフタル酸、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（変性成分）を含み、グリコール成分として、１，４－ブタンジオールを含む樹脂である。
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、１２．５モル％を超え３５モル％以下含む。変性ポリブチレンテレフタレート樹脂は、変性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、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、シリコーン系接着剤との高い接着性も付与できる。 As described above, various dicarboxylic acid components and glycol components can be used, but the modified polyalkylene terephthalate resin is particularly preferably a modified polybutylene terephthalate resin. 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.
As described above, the modified polybutylene terephthalate resin contains the modified component in excess of 12.5 mol% and 35 mol% or less with respect to the total dicarboxylic acid component. The modified polybutylene terephthalate resin has very good physical properties among the modified polyalkylene terephthalate resins, so it gives the molded resin a very good mechanical strength, electrical properties, and other physical and chemical properties. can do. Moreover, the high adhesiveness with a silicone type adhesive agent can also be provided with respect to the resin molding obtained.
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、１２．５モル％を超え３５モル％以下含む。変性ポリブチレンテレフタレート樹脂は、変性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、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、シリコーン系接着剤との高い接着性も付与できる。 As described above, various dicarboxylic acid components and glycol components can be used, but the modified polyalkylene terephthalate resin is particularly preferably a modified polybutylene terephthalate resin. 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.
As described above, the modified polybutylene terephthalate resin contains the modified component in excess of 12.5 mol% and 35 mol% or less with respect to the total dicarboxylic acid component. The modified polybutylene terephthalate resin has very good physical properties among the modified polyalkylene terephthalate resins, so it gives the molded resin a very good mechanical strength, electrical properties, and other physical and chemical properties. can do. Moreover, the high adhesiveness with a silicone type adhesive agent can also be provided with respect to the resin molding obtained.
変性ポリアルキレンテレフタレート樹脂は、本発明の効果を害さない範囲で上記されるモノマー以外のモノマー成分を含有することもできる。
The modified polyalkylene terephthalate resin can also contain monomer components other than the above-described monomers within a range not impairing the effects of the present invention.
変性ポリアルキレンテレフタレート樹脂の末端カルボキシル基量は、本発明の目的を阻害しない限り特に制限されない。変性ポリアルキレンテレフタレート樹脂の末端カルボキシル基量は、３０ｍｅｑ／ｋｇ以下が好ましく、２５ｍｅｑ／ｋｇ以下がより好ましい。かかる範囲の末端カルボキシル基量の変性ポリアルキレンテレフタレート樹脂を用いる場合には、湿熱環境下での加水分解による強度低下を受けにくくなる。
The amount of terminal carboxyl groups of the modified polyalkylene terephthalate resin is not particularly limited as long as the object of the present invention is not impaired. The terminal carboxyl group amount of the modified polyalkylene terephthalate resin is preferably 30 meq / kg or less, and more preferably 25 meq / kg or less. In the case of using a modified polyalkylene terephthalate resin having a terminal carboxyl group amount in such a range, it is difficult to receive a decrease in strength due to hydrolysis in a humid heat environment.
また、本発明のポリアルキレンテレフタレート樹脂のメルトインデックス（ＭＩ）は本発明の目的を阻害させない範囲で特に制限されない。上記メルトインデックスは５ｇ／ｍｉｎ以上１４０ｇ／ｍｉｎ以下であるのが好ましい。さらに好ましくは２０ｇ／ｍｉｎ以上１００ｇ／ｍｉｎ以下である。かかる範囲のメルトインデックスのポリアルキレンテレフタレート樹脂を用いる場合には、樹脂組成物が特に成形性に優れたものとなる。上記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の条件で測定する。なお、異なるメルトインデックスを有するポリアルキレンテレフタレート樹脂、その他の樹脂、その他の成分（添加剤等）をブレンドして、メルトインデックスを調整することもできる。
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. When a polyalkylene terephthalate resin having a melt index in such a range is used, 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.).
変性ポリアルキレンテレフタレート樹脂の製造方法は特に限定されないが、縮合反応やエステル交換反応を利用する界面重縮合、溶融重合、溶液重合等の従来公知の方法によって適宜製造することができる。また、得られた樹脂を、減圧又は不活性ガス存在下で熱処理し固相重合させることにより、樹脂の重合度をさらに高めることができる。
Although the production method of the modified polyalkylene terephthalate resin is not particularly limited, it can be suitably produced by a conventionally known method such as interfacial polycondensation using a condensation reaction or a transesterification reaction, melt polymerization, or solution polymerization. In addition, 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.
［その他の成分］
本発明の接着力改善剤は、本発明の効果を害さない範囲で、その他の樹脂、従来公知の添加剤等の他の成分を含有してもよい。 [Other ingredients]
The adhesive strength improver of the present invention may contain other components such as other resins and conventionally known additives as long as the effects of the present invention are not impaired.
本発明の接着力改善剤は、本発明の効果を害さない範囲で、その他の樹脂、従来公知の添加剤等の他の成分を含有してもよい。 [Other ingredients]
The adhesive strength improver of the present invention may contain other components such as other resins and conventionally known additives as long as the effects of the present invention are not impaired.
＜接着力改善用樹脂組成物＞
本発明の接着力改善用樹脂組成物は、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、変性成分として共重合させた変性ポリアルキレンテレフタレート樹脂（Ａ）と、未変性ポリアルキレンテレフタレート樹脂（Ｂ）とを含む。変性ポリアルキレンテレフタレート樹脂（Ａ）は、変性成分の変性量が１２．５モル％を超えて３５モル％以下である。つまり、本発明の接着力改善用樹脂組成物は、本発明の接着力改善剤を含む樹脂組成物である。
また、本発明の樹脂組成物は、下記式（Ｉ）で表される総変性量が８モル％以上である。
<Resin composition for improving adhesive strength>
The resin composition for improving adhesive force of the present invention comprises a modified polyalkylene terephthalate resin (A) obtained by copolymerizing an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modifying component, and an unmodified polyalkylene terephthalate. Resin (B). In the modified polyalkylene terephthalate resin (A), the modification amount of the modification component is more than 12.5 mol% and 35 mol% or less. That is, the adhesive force improving resin composition of the present invention is a resin composition containing the adhesive force improving agent of the present invention.
Moreover, the resin composition of this invention is 8 mol% or more of the total modification amount represented by following formula (I).
本発明の接着力改善用樹脂組成物は、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、変性成分として共重合させた変性ポリアルキレンテレフタレート樹脂（Ａ）と、未変性ポリアルキレンテレフタレート樹脂（Ｂ）とを含む。変性ポリアルキレンテレフタレート樹脂（Ａ）は、変性成分の変性量が１２．５モル％を超えて３５モル％以下である。つまり、本発明の接着力改善用樹脂組成物は、本発明の接着力改善剤を含む樹脂組成物である。
また、本発明の樹脂組成物は、下記式（Ｉ）で表される総変性量が８モル％以上である。
The resin composition for improving adhesive force of the present invention comprises a modified polyalkylene terephthalate resin (A) obtained by copolymerizing an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modifying component, and an unmodified polyalkylene terephthalate. Resin (B). In the modified polyalkylene terephthalate resin (A), the modification amount of the modification component is more than 12.5 mol% and 35 mol% or less. That is, the adhesive force improving resin composition of the present invention is a resin composition containing the adhesive force improving agent of the present invention.
Moreover, the resin composition of this invention is 8 mol% or more of the total modification amount represented by following formula (I).
変性ポリアルキレンテレフタレート樹脂（Ａ）と未変性ポリアルキレンテレフタレート樹脂（Ｂ）とを組み合わせ、且つ上記の総変性量８モル％以上に設定することで、樹脂成形体のシリコーン系接着剤に対する接着性を改善しつつ、結晶化度の低下に起因する機械的強度等の物性の低下を抑えることができる。
By combining the modified polyalkylene terephthalate resin (A) and the unmodified polyalkylene terephthalate resin (B) and setting the total modified amount to 8 mol% or more, the adhesiveness of the resin molded product to the silicone-based adhesive can be improved. While improving, the fall of physical properties, such as mechanical strength resulting from the fall of crystallinity, can be suppressed.
［変性ポリアルキレンテレフタレート樹脂（Ａ）］
変性ポリアルキレンテレフタレート樹脂（Ａ）は上記で説明したものと同様である。本発明の樹脂組成物では、変性成分の変性量が多い変性ポリブチレンテレフタレート樹脂（Ａ）を用いた方が、シリコーン系接着剤との接着性向上の効果は得られやすい。シリコーン系接着剤との接着性を向上させる観点からは、変性ポリアルキレンテレフタレート樹脂中の変性成分の変性量は１５モル％以上であることが好ましい。 [Modified polyalkylene terephthalate resin (A)]
The modified polyalkylene terephthalate resin (A) is the same as described above. In the resin composition of the present invention, the effect of improving the adhesiveness with the silicone-based adhesive is easily obtained when the modified polybutylene terephthalate resin (A) having a large amount of modification of the modifying component is used. From the viewpoint of improving the adhesiveness with the silicone-based adhesive, the modification amount of the modifying component in the modified polyalkylene terephthalate resin is preferably 15 mol% or more.
変性ポリアルキレンテレフタレート樹脂（Ａ）は上記で説明したものと同様である。本発明の樹脂組成物では、変性成分の変性量が多い変性ポリブチレンテレフタレート樹脂（Ａ）を用いた方が、シリコーン系接着剤との接着性向上の効果は得られやすい。シリコーン系接着剤との接着性を向上させる観点からは、変性ポリアルキレンテレフタレート樹脂中の変性成分の変性量は１５モル％以上であることが好ましい。 [Modified polyalkylene terephthalate resin (A)]
The modified polyalkylene terephthalate resin (A) is the same as described above. In the resin composition of the present invention, the effect of improving the adhesiveness with the silicone-based adhesive is easily obtained when the modified polybutylene terephthalate resin (A) having a large amount of modification of the modifying component is used. From the viewpoint of improving the adhesiveness with the silicone-based adhesive, the modification amount of the modifying component in the modified polyalkylene terephthalate resin is preferably 15 mol% or more.
［未変性ポリアルキレンテレフタレート樹脂（Ｂ）］
未変性ポリアルキレンテレフタレート樹脂（Ｂ）とは、テレフタル酸とアルキレングリコール又はそのエステル化物を含むグリコール成分とを重縮合して得られる樹脂である。 [Unmodified polyalkylene terephthalate resin (B)]
The unmodified polyalkylene terephthalate resin (B) is a resin obtained by polycondensation of terephthalic acid and a glycol component containing alkylene glycol or an esterified product thereof.
未変性ポリアルキレンテレフタレート樹脂（Ｂ）とは、テレフタル酸とアルキレングリコール又はそのエステル化物を含むグリコール成分とを重縮合して得られる樹脂である。 [Unmodified polyalkylene terephthalate resin (B)]
The unmodified polyalkylene terephthalate resin (B) is a resin obtained by polycondensation of terephthalic acid and a glycol component containing alkylene glycol or an esterified product thereof.
本発明の樹脂組成物中の未変性ポリアルキレンテレフタレート樹脂（Ｂ）の含有量は特に限定されず、上述の通り、式（Ｉ）に従い、総変性量が８モル％以上となるように含有量を調整すればよい。
The content of the unmodified polyalkylene terephthalate resin (B) in the resin composition of the present invention is not particularly limited, and as described above, the content is such that the total modification amount is 8 mol% or more according to the formula (I). Can be adjusted.
［（Ａ）成分と（Ｂ）成分との関係］
本発明の樹脂組成物は、上記変性ポリアルキレンテレフタレート樹脂（Ａ）を含む。変性ポリアルキレンテレフタレート樹脂は上記の通り、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（変性成分）を共重合成分として含む。これらの変性成分は、高分子に対して折れ曲がり構造を付与する。高分子が折れ曲がり構造を有すると、一般に樹脂の結晶化度が低下する。樹脂の結晶化度が低下すると樹脂成形体の機械的強度等の物性が低下する可能性がある。
本発明の樹脂組成物は、変性ポリアルキレンテレフタレート樹脂（Ａ）と未変性ポリアルキレンテレフタレート樹脂（Ｂ）とを含む。未変性ポリアルキレンテレフタレート樹脂（Ｂ）を含有すれば、変性ポリアルキレンテレフタレート樹脂（Ａ）を含んでも、樹脂組成物としての著しい結晶化度の低下は避けられ、結晶化度低下による樹脂成形体の物性低下を抑えることができる。上記の混合による結晶化度低下の抑制は、上記の好ましい含有量の範囲内であれば、結晶化度の低下は充分に抑えることができる。即ち、変性ポリアルキレンテレフタレート樹脂（Ａ）の含有量が非常に多い場合であっても（例えば、５０質量％以上９０質量％以下）、結晶化度の低下を抑制できる。なお、樹脂組成物の結晶化度を評価する方法は種々あるが、例えば、以下の数式（ＩＩ）から導出することができる。
ρ：試料の結晶密度 ρｃ：ポリアルキレンテレフタレートの結晶密度、ρａ：ポリアルキレンテレフタレートの非晶密度
（ポリブチレンテレフタレートの場合、ρｃ＝１．４０、ρａ＝１．２８、「飽和ポリエステル樹脂ハンドブック（日刊工業新聞社）」） [Relationship between component (A) and component (B)]
The resin composition of the present invention contains the modified polyalkylene terephthalate resin (A). As described above, the modified polyalkylene terephthalate resin contains an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product (modified component) as a copolymer component. These modifying components impart a bent structure to the polymer. If the polymer has a bent structure, the crystallinity of the resin generally decreases. When the crystallinity of the resin is lowered, physical properties such as mechanical strength of the resin molded body may be lowered.
The resin composition of the present invention contains a modified polyalkylene terephthalate resin (A) and an unmodified polyalkylene terephthalate resin (B). If the unmodified polyalkylene terephthalate resin (B) is contained, even if the modified polyalkylene terephthalate resin (A) is included, a significant decrease in crystallinity as a resin composition can be avoided, and Decrease in physical properties can be suppressed. If the above-mentioned mixing suppresses the decrease in crystallinity within the above-mentioned preferable content range, the decrease in crystallinity can be sufficiently suppressed. That is, even when the content of the modified polyalkylene terephthalate resin (A) is very large (for example, 50% by mass or more and 90% by mass or less), a decrease in crystallinity can be suppressed. There are various methods for evaluating the crystallinity of the resin composition. For example, it can be derived from the following formula (II).
ρ: Crystal density of sample ρ c : Crystal density of polyalkylene terephthalate, ρ a : Amorphous density of polyalkylene terephthalate (in the case of polybutylene terephthalate, ρ c = 1.40, ρ a = 1.28, “saturated polyester Resin Handbook (Nikkan Kogyo Shimbun) ")
本発明の樹脂組成物は、上記変性ポリアルキレンテレフタレート樹脂（Ａ）を含む。変性ポリアルキレンテレフタレート樹脂は上記の通り、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（変性成分）を共重合成分として含む。これらの変性成分は、高分子に対して折れ曲がり構造を付与する。高分子が折れ曲がり構造を有すると、一般に樹脂の結晶化度が低下する。樹脂の結晶化度が低下すると樹脂成形体の機械的強度等の物性が低下する可能性がある。
本発明の樹脂組成物は、変性ポリアルキレンテレフタレート樹脂（Ａ）と未変性ポリアルキレンテレフタレート樹脂（Ｂ）とを含む。未変性ポリアルキレンテレフタレート樹脂（Ｂ）を含有すれば、変性ポリアルキレンテレフタレート樹脂（Ａ）を含んでも、樹脂組成物としての著しい結晶化度の低下は避けられ、結晶化度低下による樹脂成形体の物性低下を抑えることができる。上記の混合による結晶化度低下の抑制は、上記の好ましい含有量の範囲内であれば、結晶化度の低下は充分に抑えることができる。即ち、変性ポリアルキレンテレフタレート樹脂（Ａ）の含有量が非常に多い場合であっても（例えば、５０質量％以上９０質量％以下）、結晶化度の低下を抑制できる。なお、樹脂組成物の結晶化度を評価する方法は種々あるが、例えば、以下の数式（ＩＩ）から導出することができる。
（ポリブチレンテレフタレートの場合、ρｃ＝１．４０、ρａ＝１．２８、「飽和ポリエステル樹脂ハンドブック（日刊工業新聞社）」） [Relationship between component (A) and component (B)]
The resin composition of the present invention contains the modified polyalkylene terephthalate resin (A). As described above, the modified polyalkylene terephthalate resin contains an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product (modified component) as a copolymer component. These modifying components impart a bent structure to the polymer. If the polymer has a bent structure, the crystallinity of the resin generally decreases. When the crystallinity of the resin is lowered, physical properties such as mechanical strength of the resin molded body may be lowered.
The resin composition of the present invention contains a modified polyalkylene terephthalate resin (A) and an unmodified polyalkylene terephthalate resin (B). If the unmodified polyalkylene terephthalate resin (B) is contained, even if the modified polyalkylene terephthalate resin (A) is included, a significant decrease in crystallinity as a resin composition can be avoided, and Decrease in physical properties can be suppressed. If the above-mentioned mixing suppresses the decrease in crystallinity within the above-mentioned preferable content range, the decrease in crystallinity can be sufficiently suppressed. That is, even when the content of the modified polyalkylene terephthalate resin (A) is very large (for example, 50% by mass or more and 90% by mass or less), a decrease in crystallinity can be suppressed. There are various methods for evaluating the crystallinity of the resin composition. For example, it can be derived from the following formula (II).
変性ポリアルキレンテレフタレート樹脂（Ａ）の変性成分の変性量が多くなると（例えば、変性量が２０モル％以上）、変性ポリアルキレンテレフタレート樹脂（Ａ）からなる樹脂成形体の成形は困難になる。しかし、未変性ポリアルキレンテレフタレート樹脂（Ｂ）を併用することで、変性ポリアルキレンテレフタレート樹脂（Ａ）の変性成分の変性量が多くても容易に成形することができる。この成形性を改善する効果は、変性ポリアルキレンテレフタレート樹脂（Ａ）の含有量が非常に多い場合であっても（例えば、５０質量％以上９０質量％以下）奏する。
When the modification amount of the modification component of the modified polyalkylene terephthalate resin (A) increases (for example, the modification amount is 20 mol% or more), it becomes difficult to mold a resin molded body made of the modified polyalkylene terephthalate resin (A). However, by using the unmodified polyalkylene terephthalate resin (B) in combination, it can be easily molded even if the modification amount of the modifying component of the modified polyalkylene terephthalate resin (A) is large. The effect of improving the moldability is exhibited even when the content of the modified polyalkylene terephthalate resin (A) is very large (for example, 50% by mass or more and 90% by mass or less).
［その他の成分］
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。 [Other ingredients]
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.
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。 [Other ingredients]
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.
［樹脂組成物の調製］
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。 [Preparation of resin composition]
The resin composition of the present invention can be easily prepared using general equipment and methods conventionally used for preparing resin compositions.
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。 [Preparation of resin composition]
The resin composition of the present invention can be easily prepared using general equipment and methods conventionally used for preparing resin compositions.
＜樹脂成形体＞
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は後述する。 <Resin molding>
The resin molded body of the present invention is formed by molding the resin composition of the present invention. As will be described later, the molded article of the present invention is excellent in adhesiveness with a silicone-based adhesive. The silicone adhesive will be described later.
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は後述する。 <Resin molding>
The resin molded body of the present invention is formed by molding the resin composition of the present invention. As will be described later, the molded article of the present invention is excellent in adhesiveness with a silicone-based adhesive. The silicone adhesive will be described later.
樹脂成形体を製造する際の成形方法としては、従来公知の方法を採用することができる。従来公知の成形方法としては、例えば、射出成形法、射出圧縮成形法、ガスアシスト射出成形法、加熱圧縮成形法、押出し成形法、ブロー成形法等が挙げられる。
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.
＜接合体＞
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。 <Joint>
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.
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。 <Joint>
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.
また、一対の成形体の双方を本発明の樹脂成形体にすれば、いずれの成形体もシリコーン系接着剤との接着性が高いため、接着不良の問題はより生じにくくなる。そして、双方の成形体ともにシリコーン系接着剤との接着性が高いため、より強く一対の成形体が接合する。
Further, if both of the pair of molded products are made into the resin molded product of the present invention, since any molded product has high adhesiveness with the silicone-based adhesive, the problem of poor adhesion is less likely to occur. And since both molded objects have high adhesiveness with a silicone type adhesive agent, a pair of molded object joins more strongly.
シリコーン系接着剤は、室温又は加熱により硬化する接着剤であり、従来公知のものを使用することができるが、特に、白金系触媒による付加反応で硬化が進行する付加反応型シリコーン接着剤を使用することが好ましい。
Silicone adhesive is an adhesive that cures at room temperature or by heating, and conventionally known adhesives can be used. In particular, an addition reaction type silicone adhesive that cures by an addition reaction with a platinum catalyst is used. It is preferable to do.
次いで、接合体の製造方法について説明する。接合体の製造方法は特に限定されないが、例えば、以下のような方法で製造することができる。
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。 Next, a method for manufacturing the joined body will be described. Although the manufacturing method of a joined body is not specifically limited, For example, it can manufacture by the following methods.
Here, the case where a 1st resin molding and a 2nd resin molding are joined is demonstrated. The number of molded bodies to be joined may be two or more.
First, 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. Next, 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. Thus, pressure is applied in the direction in which the first resin molded body and the second resin molded body overlap. Finally, the silicone adhesive is cured at room temperature or by heating.
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。 Next, a method for manufacturing the joined body will be described. Although the manufacturing method of a joined body is not specifically limited, For example, it can manufacture by the following methods.
Here, the case where a 1st resin molding and a 2nd resin molding are joined is demonstrated. The number of molded bodies to be joined may be two or more.
First, 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. Next, 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. Thus, pressure is applied in the direction in which the first resin molded body and the second resin molded body overlap. Finally, the silicone adhesive is cured at room temperature or by heating.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。
Hereinafter, although an example and a comparative example are shown and the present invention is explained concretely, the present invention is not limited to these examples.
＜材料＞
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。 <Material>
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.
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。 <Material>
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.
変性ポリブチレンテレフタレート樹脂１（変性ＰＢＴ１）：変性量１２．５モル％の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２（変性ＰＢＴ２）：変性量１５モル％の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）：変性量１７モル％の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）：変性量３０モル％の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） Modified polybutylene terephthalate resin 1 (modified PBT1): isophthalic acid modified polybutylene terephthalate having a modified amount of 12.5 mol% (melt index (MI): 46 g / 10 min)
Modified polybutylene terephthalate resin 2 (modified PBT2): isophthalic acid modified polybutylene terephthalate having a modification amount of 15 mol% (melt index (MI): 46 g / 10 min)
Modified polybutylene terephthalate resin 3 (modified PBT3): isophthalic acid modified polybutylene terephthalate having a modification amount of 17 mol% (melt index (MI): 30 g / 10 min)
Modified polybutylene terephthalate resin 4 (modified PBT4): isophthalic acid-modified polybutylene terephthalate having a modification amount of 30 mol% (melt index (MI): 46 g / 10 min)
変性ポリブチレンテレフタレート樹脂２（変性ＰＢＴ２）：変性量１５モル％の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）：変性量１７モル％の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）：変性量３０モル％の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） Modified polybutylene terephthalate resin 1 (modified PBT1): isophthalic acid modified polybutylene terephthalate having a modified amount of 12.5 mol% (melt index (MI): 46 g / 10 min)
Modified polybutylene terephthalate resin 2 (modified PBT2): isophthalic acid modified polybutylene terephthalate having a modification amount of 15 mol% (melt index (MI): 46 g / 10 min)
Modified polybutylene terephthalate resin 3 (modified PBT3): isophthalic acid modified polybutylene terephthalate having a modification amount of 17 mol% (melt index (MI): 30 g / 10 min)
Modified polybutylene terephthalate resin 4 (modified PBT4): isophthalic acid-modified polybutylene terephthalate having a modification amount of 30 mol% (melt index (MI): 46 g / 10 min)
［接着剤］
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」 [adhesive]
Silicone adhesive: Toray Dow Corning Silicone, trade name “SE1714”
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」 [adhesive]
Silicone adhesive: Toray Dow Corning Silicone, trade name “SE1714”
＜樹脂成形体の製造＞
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を表１、２に示す割合で、３０ｍｍφ二軸押出機（日本製鋼所製、商品名「ＴＥＸ－３０」）に投入し溶融混練後ペレットを得て、得られたペレットから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）を射出成形機（ファナック社製Ｓ２０００ｉ １００Ｂ）を用いて作製した。実施例１～６の樹脂成形体、比較例１～４の樹脂成形体が得られた。比較例１、２については未変性ポリブチレンテレフタレート樹脂ペレットをそのまま射出成形することによって成形体を得た。 <Manufacture of resin molding>
Unmodified polybutylene terephthalate resins 1 and 2 and modified polybutylene terephthalate resins 1 to 4 in the proportions shown in Tables 1 and 2 were charged into a 30 mmφ twin screw extruder (product name “TEX-30” manufactured by Nippon Steel). A pellet after melt-kneading was obtained, and a resin test piece (multipurpose test piece based on ISO 3167) used for measurement of adhesive strength described later was prepared from the obtained pellet using an injection molding machine (S2000i 100B manufactured by FANUC). . Resin molded bodies of Examples 1 to 6 and resin molded bodies of Comparative Examples 1 to 4 were obtained. For Comparative Examples 1 and 2, unmodified polybutylene terephthalate resin pellets were directly injection molded to obtain molded articles.
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を表１、２に示す割合で、３０ｍｍφ二軸押出機（日本製鋼所製、商品名「ＴＥＸ－３０」）に投入し溶融混練後ペレットを得て、得られたペレットから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）を射出成形機（ファナック社製Ｓ２０００ｉ １００Ｂ）を用いて作製した。実施例１～６の樹脂成形体、比較例１～４の樹脂成形体が得られた。比較例１、２については未変性ポリブチレンテレフタレート樹脂ペレットをそのまま射出成形することによって成形体を得た。 <Manufacture of resin molding>
Unmodified polybutylene terephthalate resins 1 and 2 and modified polybutylene terephthalate resins 1 to 4 in the proportions shown in Tables 1 and 2 were charged into a 30 mmφ twin screw extruder (product name “TEX-30” manufactured by Nippon Steel). A pellet after melt-kneading was obtained, and a resin test piece (multipurpose test piece based on ISO 3167) used for measurement of adhesive strength described later was prepared from the obtained pellet using an injection molding machine (S2000i 100B manufactured by FANUC). . Resin molded bodies of Examples 1 to 6 and resin molded bodies of Comparative Examples 1 to 4 were obtained. For Comparative Examples 1 and 2, unmodified polybutylene terephthalate resin pellets were directly injection molded to obtain molded articles.
＜接合体の作製＞
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の穴を開けたニトフロンテープ（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１～６の接合体及び比較例１～４の接合体が得られた。 <Preparation of joined body>
Cut the central part of a multi-purpose test piece in accordance with ISO 3167, and paste a nitroflon tape (thickness 0.18 mm) with a 7 mm x 7 mm hole on one resin test piece, and apply a silicone adhesive to the hole. Applied. After the application, the other resin test piece was overlaid, fixed with a clip, and bonded under conditions of 120 ° C. × 1 hour. The joined bodies of Examples 1 to 6 and the joined bodies of Comparative Examples 1 to 4 produced using a silicone-based adhesive were obtained.
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の穴を開けたニトフロンテープ（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１～６の接合体及び比較例１～４の接合体が得られた。 <Preparation of joined body>
Cut the central part of a multi-purpose test piece in accordance with ISO 3167, and paste a nitroflon tape (thickness 0.18 mm) with a 7 mm x 7 mm hole on one resin test piece, and apply a silicone adhesive to the hole. Applied. After the application, the other resin test piece was overlaid, fixed with a clip, and bonded under conditions of 120 ° C. × 1 hour. The joined bodies of Examples 1 to 6 and the joined bodies of Comparative Examples 1 to 4 produced using a silicone-based adhesive were obtained.
＜接着強度の測定＞
接合体を２３℃、５０％ＲＨの環境に２４時間以上放置し、万能試験機を用い、押し剥がし試験速度５ｍｍ／ｍｉｎの条件で、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、２に示した。
＜結晶化度の測定＞
参考までに、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を表１、２に示す割合で混合した樹脂組成物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。また、各樹脂の結晶化度は式（ＩＩ）に従い導出した。結晶化度の結果を表１、２に示した。 <Measurement of adhesive strength>
The bonded body is left in an environment of 23 ° C. and 50% RH for 24 hours or more, and the other resin test piece is peeled off at a peeling test speed of 5 mm / min using a universal testing machine, and the maximum peel strength is obtained. Was measured. The measurement results are shown in Tables 1 and 2.
<Measurement of crystallinity>
For reference, the crystallinity of a resin composition in which unmodified polybutylene terephthalate resins 1 and 2 and modified polybutylene terephthalate resins 1 to 4 were mixed in the ratios shown in Tables 1 and 2 was measured. The density of each resin was measured by an underwater substitution method (based on JIS K7112). The crystallinity of each resin was derived according to the formula (II). The results of the crystallinity are shown in Tables 1 and 2.
接合体を２３℃、５０％ＲＨの環境に２４時間以上放置し、万能試験機を用い、押し剥がし試験速度５ｍｍ／ｍｉｎの条件で、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、２に示した。
＜結晶化度の測定＞
参考までに、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を表１、２に示す割合で混合した樹脂組成物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。また、各樹脂の結晶化度は式（ＩＩ）に従い導出した。結晶化度の結果を表１、２に示した。 <Measurement of adhesive strength>
The bonded body is left in an environment of 23 ° C. and 50% RH for 24 hours or more, and the other resin test piece is peeled off at a peeling test speed of 5 mm / min using a universal testing machine, and the maximum peel strength is obtained. Was measured. The measurement results are shown in Tables 1 and 2.
<Measurement of crystallinity>
For reference, the crystallinity of a resin composition in which unmodified polybutylene terephthalate resins 1 and 2 and modified polybutylene terephthalate resins 1 to 4 were mixed in the ratios shown in Tables 1 and 2 was measured. The density of each resin was measured by an underwater substitution method (based on JIS K7112). The crystallinity of each resin was derived according to the formula (II). The results of the crystallinity are shown in Tables 1 and 2.
実施例１～６、比較例１～４の結果から明らかなように、未変性ポリブチレンテレフタレート樹脂と、変性成分の変性量が１２．５モル％を超える変性ポリブチレンテレフタレート樹脂とを特定の割合で混合し、樹脂成形体を作製することで、シリコーン系接着剤を用いて一対の樹脂成形体を接合した場合に、樹脂成形体間の接着強度が向上する。
実施例１～６、比較例２の結果から明らかなように、変性ポリブチレンテレフタレート樹脂を混合しても、結晶化度はほとんど低下しない。即ち、結晶化度低下による機械的強度等の物性低下が抑えられていることが確認された。
実施例１～３、比較例４の結果から明らかなように、本発明の接着力改善剤（変性ＰＢＴ２～４）を含有させて樹脂成形体を作製することで、シリコーン系接着剤を用いて一対の樹脂成形体を接合した場合、樹脂成形体間の接着強度が向上する。
また、実施例１～３の結果から明らかなように、接着力向上剤の変性成分の変性量が多いほど接着強度向上の効果が大きい傾向がある。 As is clear from the results of Examples 1 to 6 and Comparative Examples 1 to 4, the unmodified polybutylene terephthalate resin and the modified polybutylene terephthalate resin in which the modification amount of the modification component exceeds 12.5 mol% are in a specific ratio. When the pair of resin molded bodies are joined using a silicone-based adhesive, the adhesive strength between the resin molded bodies is improved.
As is clear from the results of Examples 1 to 6 and Comparative Example 2, even when the modified polybutylene terephthalate resin is mixed, the crystallinity is hardly lowered. That is, it was confirmed that a decrease in physical properties such as mechanical strength due to a decrease in crystallinity was suppressed.
As is apparent from the results of Examples 1 to 3 and Comparative Example 4, a resin-molded article was produced by containing the adhesive strength improver (modified PBT2 to 4) of the present invention, and a silicone adhesive was used. When a pair of resin moldings are joined, the adhesive strength between the resin moldings is improved.
Further, as is apparent from the results of Examples 1 to 3, the effect of improving the adhesive strength tends to increase as the amount of modification of the modifying component of the adhesive strength improver increases.
実施例１～６、比較例２の結果から明らかなように、変性ポリブチレンテレフタレート樹脂を混合しても、結晶化度はほとんど低下しない。即ち、結晶化度低下による機械的強度等の物性低下が抑えられていることが確認された。
実施例１～３、比較例４の結果から明らかなように、本発明の接着力改善剤（変性ＰＢＴ２～４）を含有させて樹脂成形体を作製することで、シリコーン系接着剤を用いて一対の樹脂成形体を接合した場合、樹脂成形体間の接着強度が向上する。
また、実施例１～３の結果から明らかなように、接着力向上剤の変性成分の変性量が多いほど接着強度向上の効果が大きい傾向がある。 As is clear from the results of Examples 1 to 6 and Comparative Examples 1 to 4, the unmodified polybutylene terephthalate resin and the modified polybutylene terephthalate resin in which the modification amount of the modification component exceeds 12.5 mol% are in a specific ratio. When the pair of resin molded bodies are joined using a silicone-based adhesive, the adhesive strength between the resin molded bodies is improved.
As is clear from the results of Examples 1 to 6 and Comparative Example 2, even when the modified polybutylene terephthalate resin is mixed, the crystallinity is hardly lowered. That is, it was confirmed that a decrease in physical properties such as mechanical strength due to a decrease in crystallinity was suppressed.
As is apparent from the results of Examples 1 to 3 and Comparative Example 4, a resin-molded article was produced by containing the adhesive strength improver (modified PBT2 to 4) of the present invention, and a silicone adhesive was used. When a pair of resin moldings are joined, the adhesive strength between the resin moldings is improved.
Further, as is apparent from the results of Examples 1 to 3, the effect of improving the adhesive strength tends to increase as the amount of modification of the modifying component of the adhesive strength improver increases.
Claims (7)
- 樹脂成形体とシリコーン系接着剤との接着力を改善するための、前記樹脂成形体の原料となる接着力改善用樹脂組成物であって、
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た変性ポリアルキレンテレフタレート樹脂（Ａ）と、未変性ポリアルキレンテレフタレート樹脂（Ｂ）とを含み、
（Ａ）において全ジカルボン酸成分に対する前記変性成分の変性量が１２．５モル％を超えて３５モル％以下であり、
下記式（Ｉ）で表される総変性量が８モル％以上である接着力改善用樹脂組成物。
A modified polyalkylene terephthalate resin (A) obtained by copolymerizing an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modifying component, and an unmodified polyalkylene terephthalate resin (B),
In (A), the modification amount of the modifying component with respect to the total dicarboxylic acid component is more than 12.5 mol% and not more than 35 mol%,
The resin composition for adhesive force improvement whose total modification amount represented by following formula (I) is 8 mol% or more.
- 前記変性ポリアルキレンテレフタレート樹脂（Ａ）が変性ポリブチレンテレフタレート樹脂であり、
前記未変性ポリアルキレンテレフタレート樹脂（Ｂ）が未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樹脂組成物。 The modified polyalkylene terephthalate resin (A) is a modified polybutylene terephthalate resin,
The resin composition for improving adhesive strength according to claim 1, wherein the unmodified polyalkylene terephthalate resin (B) is an unmodified polybutylene terephthalate resin. - 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樹脂組成物。 The resin composition for improving adhesive strength according to claim 1 or 2, wherein the aromatic dicarboxylic acid and / or esterified product thereof is isophthalic acid and / or esterified product thereof.
- 請求項１から３のいずれかに記載の接着力改善用樹脂組成物を成形してなる樹脂成形体。 A resin molded body obtained by molding the resin composition for improving adhesive strength according to any one of claims 1 to 3.
- 一対の成形体がシリコーン系接着剤を介して接合した接合体であって、
前記一対の成形品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。 A pair of molded bodies joined via a silicone adhesive,
The joined body in which at least one of the pair of molded products is the resin molded body according to claim 4. - 樹脂成形体とシリコーン系接着剤との接着力を改善するために前記樹脂成形体の原料に添加する接着力改善剤であって、
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た変性ポリアルキレンテレフタレート樹脂を主成分とし、
前記変性成分の変性量が１２．５モル％を超えて３５モル％以下である接着力改善剤。 An adhesive strength improver that is added to the raw material of the resin molded body in order to improve the adhesive force between the resin molded body and the silicone-based adhesive,
The main component is a modified polyalkylene terephthalate resin obtained by copolymerizing an aromatic dicarboxylic acid excluding terephthalic acid and / or an esterified product thereof as a modifying component,
An adhesive strength improver in which the modification amount of the modifying component is more than 12.5 mol% and 35 mol% or less. - 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６に記載の接着力改善剤。 The adhesive strength improver according to claim 6, wherein the aromatic dicarboxylic acid and / or esterified product thereof is isophthalic acid and / or an esterified product thereof.
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| JP2012519343A JP5773999B2 (en) | 2010-06-10 | 2011-05-31 | Adhesive strength improving resin composition, resin molded body, joined body and adhesive strength improving agent |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2011/062479 WO2011155367A1 (en) | 2010-06-10 | 2011-05-31 | Resin composition for improving adhesive strength, resin molded article, bonded article, and agent for improving adhesive strength |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5773999B2 (en) |
| WO (1) | WO2011155367A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016199100A1 (en) * | 2015-06-10 | 2016-12-15 | Sabic Global Technologies B.V. | Plastic-metal junctions and methods of making the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07126496A (en) * | 1993-10-28 | 1995-05-16 | Polyplastics Co | Polyester resin composition and molded product therefrom |
| JP2002338797A (en) * | 2001-05-11 | 2002-11-27 | Sumitomo Dow Ltd | Resin composition for film suitable for insert molding and film for insert molding prepared from the composition |
| JP2005238851A (en) * | 1999-08-30 | 2005-09-08 | Toyo Kohan Co Ltd | Printing resin film for laminating decorative panel and decorative panel using the same |
| JP2009155449A (en) * | 2007-12-26 | 2009-07-16 | Wintech Polymer Ltd | Mobile terminal part |
| JP2009155447A (en) * | 2007-12-26 | 2009-07-16 | Wintech Polymer Ltd | Polybutylene terephthalate resin composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4456392B2 (en) * | 2003-03-28 | 2010-04-28 | ウィンテックポリマー株式会社 | Laser welding resin composition and molded article |
| JP4799857B2 (en) * | 2004-12-24 | 2011-10-26 | ウィンテックポリマー株式会社 | Insert molded product |
-
2011
- 2011-05-31 JP JP2012519343A patent/JP5773999B2/en active Active
- 2011-05-31 WO PCT/JP2011/062479 patent/WO2011155367A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07126496A (en) * | 1993-10-28 | 1995-05-16 | Polyplastics Co | Polyester resin composition and molded product therefrom |
| JP2005238851A (en) * | 1999-08-30 | 2005-09-08 | Toyo Kohan Co Ltd | Printing resin film for laminating decorative panel and decorative panel using the same |
| JP2002338797A (en) * | 2001-05-11 | 2002-11-27 | Sumitomo Dow Ltd | Resin composition for film suitable for insert molding and film for insert molding prepared from the composition |
| JP2009155449A (en) * | 2007-12-26 | 2009-07-16 | Wintech Polymer Ltd | Mobile terminal part |
| JP2009155447A (en) * | 2007-12-26 | 2009-07-16 | Wintech Polymer Ltd | Polybutylene terephthalate resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016199100A1 (en) * | 2015-06-10 | 2016-12-15 | Sabic Global Technologies B.V. | Plastic-metal junctions and methods of making the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5773999B2 (en) | 2015-09-02 |
| JPWO2011155367A1 (en) | 2013-08-01 |
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