WO2008075533A1

WO2008075533A1 - Saturated polyester resin composition and adhesive composition containing the resin composition

Info

Publication number: WO2008075533A1
Application number: PCT/JP2007/072724
Authority: WO
Inventors: Madoka Furuta
Original assignee: Toagosei Co., Ltd.
Priority date: 2006-12-20
Filing date: 2007-11-26
Publication date: 2008-06-26
Also published as: JP5168150B2; TW200844176A; JPWO2008075533A1

Abstract

Disclosed is a saturated polyester resin composition which is excellent in sealing property and adhesion strength to metal materials such as copper and aluminum and resin materials such as polyethylene terephthalate. Also disclosed is an adhesive containing such a resin composition. The resin composition contains a saturated polyester resin (A) and an amorphous polyolefin resin (B). The resin composition may further contain a crystalline polyolefin resin (C). The resin composition and adhesive are suitable for sealing materials and encapsulating materials in electrical/electronic fields and automobile fields, or applications to adhesive bonding between different materials.

Description

Specification

TECHNICAL FIELD The present invention relates to a saturated polyester resin composition and an adhesive composition containing the composition.

The present invention relates to a saturated polyester resin composition containing a saturated polyester resin and an amorphous polyolefin resin, and an adhesive composition containing the resin composition. Background art

[0002] Saturated polyester resins have excellent electrical and thermal characteristics, and also have excellent adhesion to plastic materials such as polyester resins and metal materials such as copper and aluminum. Because of this characteristic, saturated polyester resins are widely used as adhesives for various parts and laminate films in the automotive and electrical / electronic fields. For example, in recent years, an aluminum vapor-deposited film and an aluminum foil laminated film have been used as food packaging materials and electrolyte sealing materials for the purpose of imparting gas barrier properties and chemical stability. Saturated polyester resin is used as an adhesive for this film.

[0003] Saturated polyester hot melt adhesives have excellent adhesive strength to aluminum. However, it is easy to form a stable oxide film on the aluminum surface. Because of this oxide film, the surface adhesion between the saturated polyester hot melt adhesive and aluminum becomes insufficient, and peeling may occur at the adhesive interface between the aluminum and the adhesive. As a result, problems such as deterioration of gas barrier uniformity and liquid leakage may occur.

[0004] Therefore, a hot melt adhesive composition in which various resin components are added to and mixed with a saturated polyester resin has been proposed. For example, Patent Document 1 proposes a saturated polyester hot melt adhesive composition in which a low density polyethylene resin or a high density polyethylene resin is added to a saturated polyester resin and an epoxy resin is added. Also

Patent Document 2 proposes a saturated polyester hot melt adhesive composition in which a phenol resin is added to a saturated polyester resin. Further, Patent Document 3 proposes a saturated polyester hot melt adhesive composition comprising a crystalline polyester resin, an amorphous polyester resin, and an epoxy resin. Patent Document 1: Japanese Patent Application Laid-Open No. 2004-269654

Patent Document 2: Japanese Patent Laid-Open No. 2003-327940

Patent Document 3: JP 2002-138269 Koyuki

Disclosure of the invention

Problems to be solved by the invention

[0006] According to the adhesive compositions described in Patent Documents 1 to 3, the peel strength between aluminum and the adhesive is improved compared to the saturated polyester resin alone, which is the main component. In the adhesive composition described in Patent Documents 1 to 3, the peeling at the bonding interface between aluminum and the adhesive has not been solved. Therefore, a film using the adhesive composition is inferior in gas barrier properties and liquid sealing reliability.

[0007] The present invention is an invention for improving the constitution of a saturated polyester resin composition. An object of the present invention is to provide a composition capable of improving the adhesive strength and the peeled state of the adhesive interface with respect to metal materials such as copper and aluminum and resin materials such as polyethylene terephthalate.

Means for solving the problem

[0008] The present inventors have intensively studied in view of the above problems. As a result, the present inventors have found that the above problems can be solved by blending a specific polyolefin resin with a saturated polyester resin, and have completed the present invention.

That is, the present invention is as follows.

[1] A saturated polyester resin composition comprising a saturated polyester resin (A) and an amorphous polyolefin resin (B).

[2] The content of the amorphous polyolefin resin (B) is 100% by mass relative to the total amount of the saturated polyester resin (A) and the amorphous polyolefin resin (B); The saturated polyester resin composition according to the above [1], which is in mass%.

[3] The saturated polyester resin composition according to [1], further including a crystalline polyolefin resin (C).

[4] The saturated polyester resin composition according to the above [3], wherein the crystalline polyolefin resin (C) has a crystal heat of fusion of 50 j / g or more. [5] The saturated polyester resin composition according to the above [3], wherein the heat of fusion of crystals of the amorphous polyolefin resin (B) is 10 j / g or less.

[6] The non-crystalline polyolefin resin is based on 100% by mass of the saturated polyester resin (A), the non-crystalline polyolefin resin (B) and the crystalline polyolefin resin (C). The saturated polyester resin composition according to [3] above, wherein the content of (B) is! ~ 30 mass%, and the content of the crystalline polyolefin resin (C) is 3-30 mass%. [7] The saturated polyester resin composition according to [3], wherein the ratio of the crystalline polyolefin resin (C) to 100 parts by mass of the amorphous polyolefin resin (B) is 60 to 250 parts by mass. object.

[8] An adhesive composition comprising the saturated polyester resin composition according to 1 above, wherein any one of the above [1] to [7] is used.

[9] A hot-melt adhesive comprising the saturated polyester resin composition according to any one of [1] to [7] above.

The invention's effect

[0010] An adhesive member using the saturated polyester resin composition of the present invention as an adhesive (hot melt adhesive or the like) has excellent adhesion performance. As a result, the adhesive strength to metal materials such as copper and aluminum and resin materials such as polyethylene terephthalate can be improved, and the fracture mode can be improved. In particular, the adhesive strength and fracture morphology at low temperatures are improved. Further, since the interface peeling state between the adhesive and the adherend is improved, it is possible to obtain an adhesive member having excellent sealing properties and gas noisy properties.

BEST MODE FOR CARRYING OUT THE INVENTION

[0011] One embodiment of the present invention will be described as follows. However, the present invention is not limited to this.

[0012] The saturated polyester resin composition of the present invention (hereinafter referred to as "resin composition") comprises a saturated polyester resin (A) (hereinafter also referred to as "resin component (A)") and an amorphous substance. And a porous polyolefin resin (B) (hereinafter also referred to as “resin component (B)”). Further, the adhesive composition and hot melt adhesive of the present invention are characterized by containing the resin composition of the present invention. [0013] [1] Resin component (A)

There are no particular limitations on the acid component and the polyol component, which are monomers constituting the resin component (A). As the acid component, aromatic dibasic acids, aliphatic dibasic acids, alicyclic dibasic acids, and ester formers thereof can be used. Specific examples of aromatic dibasic acids and their ester formers include terephthalic acid, isophthalic acid, phthalic anhydride

, A naphthalenedicarboxylic acid and / 3-naphthalenedicarboxylic acid, and ester formers thereof (for example, C1-C3 alkyl esters such as methyl ester and ethyl ester) and the like. Specific examples of the aliphatic dibasic acid and its ester former include succinic acid, dartaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecylenic acid, and dodecanedioic acid, and These ester formers (for example, C1-C3 alkyl esters such as methyl ester and ethyl ester) and the like can be mentioned. Specific examples of the alicyclic dibasic acid and its ester former include 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.

[0014] Among the above acid components, terephthalic acid and its ester forming body strength are preferred in terms of adhesive strength. The proportion of terephthalic acid is preferably 30 mol% or more with respect to the total acid components. When the terephthalic acid component is less than 30 mol%, the cohesive strength and hardness of the resin composition of the present invention are insufficient, and the adhesive strength is lowered. The upper limit of the proportion of terephthalic acid is usually 100 mol%, preferably 90 mol%, more preferably 80 mol%, based on the total acid component.

[0015] In addition, a polycarboxylic acid such as trimellitic acid and pyromellitic acid can be used in combination as the acid component. The polyvalent carboxylic acid can be used in combination within a range where gelation does not occur during polyester synthesis or within a range where adhesive strength is not impaired. The polyvalent carboxylic acid can be used, for example, in a range of 5 mol% or less with respect to the total acid component. The lower limit of the proportion of the polyvalent carboxylic acid is usually 0.1 mol% relative to the total acid component, preferably 0.5 mole ^_0/0, more preferably 1 mol%.

As the polyol component, for example, aliphatic glycols and alicyclic glycol dihydric alcohols and polyhydric alcohols can be used. The above aliphatic glycols may be used alone or in combination of two or more. The alicyclic glycol is a single type Two or more types may be used in combination. As the polyol component, one or more of the above aliphatic glycols and one or more of the above alicyclic glycols may be used in combination.

[0017] The aliphatic glycol includes, for example, an aliphatic glycol having 2 to 14 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and more preferably 2 to 8 carbon atoms. The Specific examples of the aliphatic glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4 butanediol, 1,5-pentanzone, 1,6-hexanosanol, 1,8-octanesanol, 1,9-nonanediol, neopentyl glycol, 3 methylpentanediol, 2,2,3 trimethylpentanediol, diethylene glycol, triethylene glycol, and dipropylene glycol Is mentioned. Specific examples of the alicyclic glycol include 1,4 cyclohexanedimethanol and hydrogenated bisphenol A.

[0018] In addition, as the polyol component, polyhydric alcohols such as glycerin, trimethylolethane, trimethylol bread, and pentaerythritol can also be used. For example, the polyhydric alcohol can be used within a range of 5 mol% or less with respect to the total alcohol components. The lower limit of the proportion of the polycarboxylic acid is usually 0 - 1 mole ^_0/0 relative to the total alcohol component, preferably 0 - 5 mole ^_0/0, more preferably 1 mole ^_0/0 It is.

[0019] The dihydric alcohol is preferably 1,4 butanediol. The proportion of 1,4 butanediol is preferably 30 mol% or more based on the total alcohol components. When the proportion of 1,4-butanediol is less than 30 mol%, the obtained resin component (A) lacks cohesive strength and has low adhesive strength and insufficient heat resistance.

[0020] The melting point of the resin component (A) indicated by the heat of fusion peak temperature is preferably 50 to 200 ° C, more preferably 60 to 150 ° C. The “melting heat peak temperature” is the main endothermic peak temperature at which the heat of fusion measured by a differential scanning calorimeter (hereinafter also referred to as “D SCj”) is not less than lj / g. When it is less than C, the heat resistance of the resin composition of the present invention is insufficient, and when it exceeds 200 ° C., the coating temperature and the adhesion temperature are increased, so that the thermal deterioration of the adhesive base sheet occurs, It causes adhesion failure.

[0021] The resin component (A) can be synthesized and produced by an ordinary method. Resin component (A) Examples of the production method include (1) a melt polymerization method in which raw materials and a catalyst are charged and heated at a temperature equal to or higher than the melting point of the product, (2) a solid phase polymerization method in which polymerization is performed at a temperature lower than the melting point of the product, A solution polymerization method using is used. Any method may be adopted as a method for producing the resin component (A). However, in order to obtain a polyester having an appropriate degree of polymerization that meets the object of the present invention, the melt polymerization method is preferred from the viewpoint of economy. The resin component (A) is produced, for example, by an ester exchange method or a direct esterification method.

[0022] In the resin composition, adhesive, and hot melt adhesive of the present invention, the content of the resin component (A) is based on the total amount of the resin components (A) and (B). 50 to 99% by mass is preferable, and 55 to 95% by mass is more preferable, and 60 to 90% by mass is particularly preferable. When the ratio of the resin component (A) is less than 50% by mass, the strength of the resin composition itself of the present invention is lowered, so that the resulting peel strength tends to be lowered. On the other hand, when it exceeds 99% by mass, the wettability to the adhesive substrate is lowered, and interfacial peeling is likely to occur.

[0023] [2] Resin component (B)

The resin component (B) has a function of improving adhesion to an adhesive substrate such as aluminum. As a means to improve the adhesion to the adhesive substrate, [1] improvement of the wettability of the adhesive to the adhesive substrate, and [2] flexibility of the adhesive composition, to the interface between the adhesive and the adhesive substrate. It is important to prevent stress concentration of the peeling stress. When the crystalline polyolefin resin has a low crystallinity in the heat-melted state, the surface free energy is low, so that the wetness to the adhesive substrate is good. However, the cooled and solidified crystalline polyolefin resin increases the surface free energy as it crystallizes, and does not get wet to the adhesive substrate, and naturally peels off. On the other hand, amorphous polyolefin resin has low surface free energy even in a cooled and solidified state, and therefore can improve adhesion to an adhesive substrate. Furthermore, since the resin component (B) is highly flexible even at room temperature, it is possible to prevent stress concentration at the interface between the adhesive and the adhesive base material against the peeling stress. The present invention is not an explanation for defining the function and range of the resin component (B), nor is it an explanation for limiting the function and range of the resin component (B)! /, ).

[0024] The main monomer component constituting the resin component (B) is a bull monomer having an unsaturated double bond. Specific examples of the bull monomer include polyethylene and polypropylene. Examples include α-olefin having 2 to 20 carbon atoms such as pyrene, and olefin monomer power such as alicyclic olefin monomer, and one or more of these monomer groups. Preferred examples of the bulmonomer include monomers having propylene, ethylene, and 1-butene as main components, as shown in, for example, JP-A-11 80233 and JP-A-2000-198820. When the main monomer constituting the resin component (Β) is a monomer other than the olefin-based monomer, the surface free energy of the resin composition of the present invention is increased, the adhesion to the adhesive substrate is lowered, and the interfacial peeling state It is easy to become. In addition, the above bulle monomers may be used alone or in combination of two or more.

[0025] Further, as the monomer component constituting the resin component (i), one or more of other monomers can be used within a range not impairing the object of the present invention. Examples of the other monomers include aromatic butyl monomers such as styrene and α-methyl styrene, acrylic ester butyl monomers such as ethyl acrylate, and carboxyl group-containing butyl monomers such as acrylic acid and phthalic anhydride. Is mentioned.

[0026] The resin component (Β) is characterized by low crystallinity! /. Here, the “crystallinity” is indicated by the amount of heat of crystallization measured by DSC or the amount of heat of fusion measured by DSC. The resin component (Β) preferably has a heat of fusion measured by DSC of 10 j / g or less or a heat of crystallization of 10 j / g or less. In particular, the resin component (B) preferably has a heat of fusion of 5 j / g or less or a heat of crystallization of 5 j / g or less. Furthermore, the resin component (B) preferably has a heat of fusion of 3 j / g or less or a heat of crystallization of 3 j / g or less. When the heat of fusion or crystallization calorie of the resin component (B) exceeds 0j / g, the crystallinity increases and the wettability to the adhesive substrate decreases, and the peeling stress concentrates on the adhesive interface. Therefore, it is easy to be in a state of interface peeling. When the resin component (B) is completely amorphous, the heat of fusion or heat of crystallization is Oj / g. The heat of fusion or crystallization of the resin component (B) can be from 0 to 10 j / g, and the heat of fusion or crystallization of the resin component (B) can be from 0 j / g to the upper limit of each of the above. It can also be up to i.

[0027] There is no particular limitation on the melt viscosity of the resin component (B)! The melt viscosity can be expressed, for example, as a melt index value (hereinafter also referred to as “MI value”). The Ml value of resin component (B) (measured under the conditions of a temperature of 230 ° C and a load of 21.2 N) is usually 0.5 to 150 g / 10 min, more preferably Is! ~ 120g / 10min. When the MI value is less than 0.5 g / 10 min, the melt viscosity is too high, so that the mixing with the resin component (A) becomes uneven and stable adhesive strength cannot be obtained. On the other hand, if the Ml value exceeds 150 g / 10 min, the resin composition becomes too soft and the adhesive strength decreases.

[0028] In the resin composition, adhesive and hot melt adhesive of the present invention, the content of the resin component (B) is the total amount of the resin component (A) and the resin component (B) 100. It is preferable that it is! ~ 50 mass% with respect to the mass%. It is more preferable that the mass is 5 to 45 mass% than S, 10 to 40 mass% is more preferable, and 10 to 30 mass% is more preferable. A preferred range is 10 to 25% by mass. If the content of the resin component (B) is less than 1% by mass, the interfacial delamination tends to occur because the wettability to the adhesive substrate is low! On the other hand, when it exceeds 50% by mass, the strength of the composition itself is lowered, so that the peel strength obtained is lowered.

[0029] [3] Crystalline polyolefin resin (C)

The resin composition, adhesive, and hot melt adhesive of the present invention preferably further contain a crystalline polyolefin resin (C) (hereinafter also referred to as “resin component (C)”). The resin component (C) plays a role of preventing peeling stress concentration on the adhesive substrate interface. The resin component (C) is usually present in a finely dispersed state in the adhesive composition. Since the wettability between the surface of the dispersed particles and the interface of the resin component (A), which is the main component, is low !, a peeling stress is applied to the interface between the dispersed particles of the resin component (A) and the resin component (C). Can be dispersed. As a result, the peeled state between the adhesive and the adhesive substrate interface can be improved (note that this description is an explanation for helping the understanding of the present invention. The present invention is based on the resin component (C)). It is not an explanation for defining the function and range of the resin, nor is it an explanation for limiting the function and range of the resin component (C).) Therefore, as the resin component (C), the crystallinity is high and the polyolefin resin is preferred so that the surface free energy of the resin component (C) is high.

[0030] As described above, the resin component (C) is preferably a polyolefin resin having a high degree of crystallinity.

More specifically, for example, the resin component (C) preferably has a heat of fusion of 50 J / g or more or a crystallization caloric power of 0 j / g or more as measured by DSC. In particular, the resin component (C) preferably has a heat of fusion of 80 j / g or more or a heat of crystallization of 80 j / g or more (usually 220 j / g or less). That is, the heat of fusion or crystallization of the resin component (C) is 50-2. 20j / g, and 80 (the above lower limit) to 220j / g. When the heat of fusion or crystallization of the resin component (C) is less than 50 j / g, the interfacial adhesion between the resin component (A) and the particle surface of the resin component (C) is increased. Peeling easily occurs at the adhesive substrate interface.

[0031] The component constituting the resin component (C) is selected from one or more of bulle monomers having an unsaturated double bond. Examples of the bulle monomer include olefin bule monomers having 2 to 20 carbon atoms such as polyethylene and polypropylene. Preferred are high-density polyethylene resins containing ethylene as a main component (for example, density 0.94 to 0.97 g / cm ³ ) and low-density polyethylene resin (for example, density 0.91-0.93 g / cm ³ ). . More preferably, the bull monomer is low density polyethylene.

[0032] The melt viscosity of the resin component (C) is not particularly limited! /. The melt viscosity can be expressed, for example, as an Ml value. The Ml value (measured under conditions of a temperature of 190 ° C and a load of 21.2 N) of the resin component (C) is usually 0.5 to 150 g / 10 min, preferably;! To 120 g / 10 min. When the Ml value is less than 5 g / 10 min, the melt viscosity is too high, so the mixing with the saturated polyester resin composition becomes uneven and stable adhesive strength cannot be obtained. On the other hand, if the Ml value exceeds 150 g / 10 min, the adhesive composition becomes too soft and the adhesive strength decreases.

[0033] When the resin composition, adhesive, and hot melt adhesive of the present invention contain the resin components (B) and (C), the content of each resin component is not particularly limited. The content of each resin component can be set within an arbitrary range. However, in order to obtain the full effect of including both resin components, when the total content of the resin components (A) to (C) is 100% by mass, the resin component (B) is: -30% by mass, and the resin component (C) is preferably 3-30% by mass. In particular, the resin component (B) is more preferably 5 to 25% by mass, and the resin component (C) is more preferably 5 to 25% by mass. Further, the resin component (B) is more preferably 10 to 20% by mass, and the resin component (C) is more preferably 10 to 20% by mass.

[0034] Further, the ratio of the resin components (B) and (C) is not particularly limited. For example, the ratio of the resin component (C) to 100 parts by mass of the resin component (B) 100-250 parts by mass, preferably 70-230 parts by mass, and more preferably 75-200 parts by mass.

[0035] [4] Other In the resin composition, adhesive, and hot melt adhesive of the present invention, one or more arbitrary tackifiers can be used as long as the object of the present invention is not impaired. The above-mentioned tackifier is usually effectively used for adjusting the heat resistance and elastic modulus of the resin composition, adhesive and hot melt adhesive of the present invention, and adjusting the adhesion to the adhesive substrate. As said tackifier, arbitrary resin-type tackifiers are mentioned, for example. Examples of the resin type tackifier include (1) epoxy resin type tackifiers such as bisphenol type epoxy resin, phenol type epoxy resin, nopolac type epoxy resin, and cresol nopolac type epoxy resin, (2 ) Terpene resin, terpene phenol resin, aromatic modified terpene resin, terpene resin type tackifier such as hydrogenated terpene resin, (3) rosin modified resin type tackifier such as rosin modified phenol resin, and (4) fat It is possible to use petroleum resin type tackifiers such as aromatic petroleum resins, alicyclic petroleum resins, and aromatic petroleum resins. The above resin-type tackifiers may be used alone or in combination of two or more. The R & B softening point of the resin-type tackifier is preferably 50 to 180 ° C. The R & B softening point is a resin physical property defined by JIS K-6863-1994.

[0036] The amount of the tackifier (for example, the resin-type tackifier) used is usually 30 parts by mass or less (for example, 0.;!) With respect to 100 parts by mass of the resin composition of the present invention. To 30 parts by mass), preferably 20 parts by mass or less. The lower limit of the amount of the tackifier used is usually 0.1 parts by weight, preferably 0.5 parts by weight, and more preferably 1 part by weight with respect to 100 parts by weight of the resin composition of the present invention. .

[0037] In the resin composition, adhesive, and hot melt adhesive of the present invention, any filler can be used as long as the object of the present invention is not impaired. Usually, the filler is effectively used for adjusting the heat resistance, elastic modulus, blocking resistance, productivity and the like of the resin composition of the present invention. Examples of the filler include (1) talc, organic surface-treated talc, clay, heavy calcium carbonate, light calcium carbonate, silica, fumed silica, zinc oxide, magnesium hydroxide, aluminum hydroxide, titanium oxide, and glass. It is possible to use inorganic compound type fillers such as fibers, smectite type layered silicate compounds, and organically treated smectite type layered silicate compounds, and (2) organic compound type fillers such as carbon black and chemical fibers. . The above fillers may be used alone or in combination of two or more. Yes

[0038] The amount of the filler used is usually 30 parts by mass or less (eg, 0.;! To 30 parts by mass), preferably 20 parts by mass with respect to 100 parts by mass of the resin composition of the present invention. Below, more preferably 10 parts by mass or less. The lower limit of the amount of the filler used is usually 0.1 parts by weight, preferably 0.5 parts by weight, and more preferably 1 part by weight with respect to 100 parts by weight of the resin composition of the present invention.

[0039] In the resin composition, adhesive, and hot melt adhesive of the present invention, any stabilizer can be used as long as the object of the present invention is not impaired. Usually, the stabilizer is effectively used for suppressing the thermal decomposition or hydrolysis of the resin composition of the present invention and adjusting the stability of the adhesive performance. Examples of the stabilizer include hydrolysis inhibitors such as polycarpositimide, and antioxidants such as phenolic antioxidants, phosphite antioxidants, and thioteric antioxidants. The above stabilizers may be used alone or in combination of two or more.

[0040] The amount of the stabilizer used is usually 10 parts by mass or less (for example, 0.;! To 10 parts by mass), preferably 5 parts by mass or less, with respect to 100 parts by mass of the resin composition of the present invention. . The lower limit of the amount of the stabilizer used is usually 0.1 parts by weight, preferably 0.5 parts by weight, and more preferably 1 part by weight with respect to 100 parts by weight of the resin composition of the present invention.

[0041] In the resin composition, adhesive, and hot melt adhesive of the present invention, any coupling agent can be used as long as the object of the present invention is not impaired. The coupling agent usually works on the surface of the adhesive substrate of the resin composition, adhesive, and hot melt adhesive of the present invention, and is effectively used for adjusting the heat and humidity resistance. The above coupling agents may be used alone or in combination of two or more. For example, a silane force coupling agent, an aluminum coupling agent, and a titanate coupling agent are used as the coupling agent.

[0042] Specific examples of the silane coupling agent include alkyl-based silane coupling agents such as dimethyldimethoxysilane, amino group-containing silane coupling agents such as 3-aminopropyltriethoxysilane, and 3-glycol. Epoxy group-containing silane coupling agents such as sidoxypropyltrimethoxysilane, and bur group-containing silane cuts such as butyltriacetoxysilane Examples include pulling agents. Specific examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate. Specific examples of the titanate coupling agent include isopropyl triisostearoyl titanate. These additives may further improve the characteristics of the present invention and can be used as appropriate.

[0043] The amount of the coupling agent used is 5 parts by mass or less (for example, 0 .;! To 5 parts by mass), preferably 3 parts by mass or less, with respect to 100 parts by mass of the resin composition of the present invention. More preferably, it is 2 parts by mass or less. The lower limit of the amount of the coupling agent used is usually 0.1 parts by weight, preferably 0.5 parts by weight, and more preferably 1 part by weight with respect to 100 parts by weight of the resin composition of the present invention.

[0044] In the resin composition, adhesive, and hot melt adhesive of the present invention, any other additive may be used alone or in combination as long as the object of the present invention is not impaired. . For example, the resin composition of the present invention may use one or more of flame retardants such as brominated flame retardants and phosphorus flame retardants, ultraviolet absorbers, plasticizers, and crystal nucleating agents. it can.

[0045] The method for producing the resin composition of the present invention is not particularly limited. The resin composition of the present invention can be obtained by mixing the resin component (A), the resin component (B), and the resin component (C) by any method. The resin composition of the present invention includes, for example, a single-screw extruder, a mesh-type co-directional parallel-shaft twin-screw extruder, a mesh-type hetero-directional parallel-axis twin-screw extruder, and a mesh-type hetero-directional oblique-axis bi-axial extrusion. Extruder, non-matching twin screw extruder, incomplete mating twin screw extruder, conida single screw extruder, planetary gear extruder, transfer mix extruder, ram extruder, roller extruder, etc. It can be obtained by mixing each raw material with a kneader or the like. Prior to the mixing, the raw materials can be premixed using a Henschel mixer or a tumbler. In addition, there is no limitation in particular in the shape and property of each raw material component of the resin composition of this invention. A raw material component having an arbitrary shape or property such as a pellet shape, a powder shape, and a liquid shape can be used.

[0046] The form in the case of using the resin composition of the present invention as an adhesive may be any form without particular limitation. For example, when the resin composition of the present invention is used as an adhesive, as a pellet shape, a powder shape, a sheet 'film shape, a rod shape, a solution state dissolved in a solvent, etc. Use with power.

[0047] The use form of the resin composition of the present invention is not particularly limited! /. For example, the resin composition of the present invention can be used in the form of pellets, powders, sheets'films, rods, and dissolved nights dissolved in a solvent.

[0048] The resin composition, adhesive, and hot-melt adhesive of the present invention are excellent in adhesive strength, particularly adhesion, to various metals and plastic materials. The resin composition, adhesive and hot melt adhesive of the present invention can be used in various fields. For example, the resin composition, the adhesive, and the hot melt adhesive of the present invention can be used as an adhesive, a sealing material, and a sealing material for parts in the electronic / electrical field. The resin composition, adhesive and hot melt adhesive of the present invention can be used as an adhesive between laminated films or laminated sheets in the packaging field. Furthermore, the resin composition, the adhesive, and the hot melt adhesive of the present invention can be used as an adhesive for interior materials and a sheath material for wire harness in the automotive field.

Example

[0049] (Production of saturated polyester resin)

Into a four-flask equipped with a stirrer, nitrogen inlet tube, distillation tube and thermometer, dimethino terephthalate 0.6 monole, 1,4-butanediol 1.6 monole, 1,6-hexanediol 0.2 monole , and was charged with tetra-η- butyl titanate 0 · ² X 10- 2 mol of a catalyst. Next, the temperature was increased while introducing nitrogen, and methanol was distilled off at 130 to 200 ° C. Then, 0.1-monoole of isobutanolic acid and 0.25 monolecate of cenotic acid were calorie-free and 200-240 °. C distilled water. Thereafter, the reaction was continued for 3 hours under reduced pressure of ImmHg at 250 ° C. while gradually reducing the pressure to obtain a saturated polyester resin (A-1).

[0050] The melting point of the saturated polyester resin (A-1) (measured using DSC at a temperature rise of 10 ° C / min) is 135 ° C, the glass transition point is 18 ° C, and the melt flow The rate (measured in accordance with JIS-K-7660-1981, 190. C, load 21.2N) was 80 g / 10mii. Further, the monomer composition of the saturated polyester resin (A-1) was analyzed by NMR analysis. The monomer composition was terephthalic acid / isophthalic acid / sebatic acid / 1,4-butanediol / 1,6-hexanediol / norre = 60/15/25/80/20 in molar ratio. [0051] (Production Method of Composition 1)

As the resin component (A), 1424 g of saturated polyester resin (AI) and as the resin component (B), “Tufselen SCC-24” (hereinafter also referred to as “amorphous PO-1”) manufactured by Sumitomo Chemical Co., Ltd. As the resin component (C), 292 g of low density polyethylene (LDPE) (“Geylex LD JM910” manufactured by Nippon Polyolefin Co., Ltd.) was used. Measured by DSC (using RDC220 manufactured by Seiko Instruments Inc., sample amount: 8 mg, temperature rising condition: 10 ° C / min, under air atmosphere) by the method according to JIS-K7122 The heat of fusion was measured and found to be 2.5 j / g.

[0052] The resin component (A) ~ (C) previously mixed uniformly, and poured into Ikegai Corp. 30 mm ² screw extruder "PCM-30", was melt-mixed at 160 ° C. The molten resin discharged in the form of a strand from the extruder was cooled and solidified in a water tank. The solidified resin was cut into a pellet shape with a pelletizer, and 500 g of composition 1 was obtained.

[0053] (Composition / Method of preparing copper test piece)

Composition 1 was hot pressed (lkg / cm ² , 30 seconds) at 180 ° C. to produce a sheet having a thickness of approximately 100 111 (80 to 120 m). The obtained sheet was cut into a width of 25 mm and a length of 50 mm to prepare an adhesive sheet. Also, a copper plate (material C-1100P, thickness 150 ^ m) as an adhesive substrate was cut into a width of 25 mm and a length of 75 mm. The adhesive sheet is sandwiched between two adhesive substrates so that the length of the tension gripping margin remains approximately 25 mm, and the composition is heated and pressed at 180 ° C, 0. IMPa for 30 seconds. / A copper specimen was created.

[0054] (Adhesive strength test to copper substrate)

(Example 1)

Fix the composition 1 / copper test piece to the chuck of a tensile tester (Shimadzu Autograph “DSS-500”) so that the composition 1 / copper test piece is T-shaped. The tensile load was measured under the condition of a tensile speed of 5 mm / min. The tensile strength under this condition was 11. Okgf. Moreover, the tensile strengths when the tensile speed was 20 mm / min and 50 mm / min were 15.8 kgf and 16.3 kgf, respectively. Furthermore, the tensile strength when the tensile speed was 200 mm / min was 15.6 kgf, and when the peeled form was visually confirmed, cohesive failure of the adhesive was observed. [0055] (Comparative Example 1)

Saturated polyester-based resin (A-1) 1666g and resin component (C) "Di-Ilex LDJH527J 334g were uniformly mixed to obtain composition 2 in the same manner as composition 1. Composition 1 / copper test piece and A composition 2 / copper test piece was prepared under the same conditions, and the adhesive strength was measured in the same manner as in Example 1. As a result, the tensile speed was 5 mm / min, 20 mm / min, 50 mm / min. And 200 mm / min, the tensile strengths were 5.2 kgf, 6.7 kgf, 7.8 kgf, and 11.4 kgf, respectively. When confirmed, interfacial peeling at the interface between the copper test piece and the adhesive was observed.

[0056] Compared to Comparative Example 1, Example 1 was found to have a tensile strength that was about twice as high. Further, in Example 1, cohesive failure was more likely to occur than interfacial peeling. From this result, it can be judged that by adding the amorphous polyolefin resin (resin component (B)) to the saturated polyester resin, the adhesion to the copper base material is increased, and the adhesion performance and the sealing performance are enhanced.

[0057] (Composition 3 ~; method for producing 1 1)

Compositions 3 to 11 were obtained in the same manner as the production method of Composition 1 with the composition blending ratio shown in Table 1.

[0058] (Examples 2-3 and 13-; 14, and Comparative Example 2)

Compositions / copper specimens were prepared using compositions 3-5 and 10-; Tensile strength was measured in the same manner as in Example 1, and the peel form was visually confirmed. The results are shown in Examples 2 to 3 and 13 to; 14 and Comparative Example 2 in Table 2.

[0059] [Table 1]

§

table 1

Amorphous PO— 1 ： Sumitomo Chemical Co., Ltd. “Tough Selenium SCC24J, Ml value = 124 _g / 10 min (Temperature 230 ° C, Load 21.2N), Heat of fusion 2.5J / _g Amorphous PO— 2: Sumitomo Chemical Co., Ltd. , Ml value = 3g 10min (Temperature 230 ° C, Load 21.2N), Heat of fusion 3.2JZg Amorphous PO—3: “Tough selenium H5002 丄 Ml value = 10g / 10min (temperature 230 ° C, load) 21.2N), heat of fusion 1.9J / g LDPE: crystalline polyethylene resin (low density polyethylene), heat of fusion 112J / g

Epoxy resin: Bisphenol A type epoxy resin, R & B softening point 138¾ was used.

[0061] Comparative Example 2 is an example using an epoxy resin type tackifier. According to Table 2, compared with Comparative Example 1, the tensile strength was slightly increased under the tensile speed condition of 5 mm / min.

On the other hand, in Examples 2 and 3, it was confirmed that the tensile strength was about twice as high as that in Comparative Examples 1 and 2. In Examples 2 and 3, cohesive failure was more likely to occur than interfacial peeling. From this result, the adhesion performance and the sealing performance with high adhesion to the copper base material are high. It can be judged that it became. Furthermore, in Examples 1 to 3, although the melt viscosity of the amorphous polyolefin resin used was 124 g / 10 min, 3 g / 10 min, and lOg / 10 min, respectively, The adhesion was excellent.

[0063] (Adhesive strength test to aluminum substrate)

(Examples 4 to 6 and Comparative Example 3)

A composition / aluminum test piece was prepared in the same manner as the copper test piece, except that an aluminum plate (material AL5052, thickness 300 m) was used as the adhesive substrate. Tensile strength was measured in the same manner as in Example 1, and the peel form was visually confirmed. The results are shown in Table 3.

[0064] [Table 3]

According to Table 3, Example 4 and Example 5 have a cohesive failure mode regardless of the melt viscosity of the amorphous polyolefin resin, compared with Comparative Example 3 using an epoxy resin tackifier. It was confirmed that it has excellent adhesion to aluminum and easy sealing. In Example 6, although the amount of the amorphous polyolefin resin added was smaller than that in Example 5, cohesive failure was more likely to occur in aluminum than in Comparative Example 3. Excellent wearability and sealability!

[0066] (Adhesive strength test to polyethylene terephthalate film)

(Examples 7 to 10; and Comparative Example 4)

A composition / PET film test piece was prepared in the same manner as the copper test piece, except that a 100 Hm thick polyethylene terephthalate film (hereinafter also referred to as “PET film”) was used as the adhesive substrate. . Tensile strength was measured in the same manner as in Example 1, and the peel form was visually confirmed. The results are shown in Table 4.

[0067] [Table 4]

According to Table 4, in Example 7, compared to Comparative Example 4 using an epoxy resin-based tackifier, the fracture form in which the tensile strength is twice or more is easy to cause cohesive failure. From this result, it can be seen that the resin composition containing the amorphous polyolefin resin has better adhesion to polyethylene terephthalate and sealability than the resin composition containing the epoxy resin tackifier. It was confirmed. On the other hand, in Example 8 and Example 9, polyethylene terephthalate is more susceptible to cohesive failure than Comparative Example 4 regardless of the amount of amorphous polyolefin resin added.

It was excellent in adhesiveness to the fracture surface and sealability. Further, in Example 10, the amount of the crystalline polyethylene resin used is less than that in Example 7! / The composition is used! /, The cohesive failure is likely to occur, and there is an adverse effect on the adhesion and sealability. It was a powerful force.

[0069] (Temperature dependency test of adhesive strength)

(Examples 11-; 12, and Comparative Examples 5-6)

For the composition / PET film test piece shown in Table 5, measure the tensile strength when the temperature condition of the tensile test is set to 40 ° C and 5 ° C, and the tensile speed is 200 mm / min. The peeling form was confirmed visually. The results are shown in Table 5.

[0070] [Table 5] Table 5

Form

Interfacial peeling between adhesive and adhesive substrate

Adhesive cohesive failure

Destruction of PET film

[0071] According to Table 5, Example 11 and Example 12 have high adhesion to the PET film substrate even at 40 ° C and 5 ° C. Further, in Example 11 and Example 12, cohesive failure and material failure of the PET film substrate were observed. On the other hand, in Comparative Example 5 and Comparative Example 6, since the adhesion to the PET film substrate was insufficient, the adhesive strength was low and the peeling form was interfacial peeling.

Industrial applicability The resin composition of the present invention and an adhesive such as a hot melt adhesive containing the resin composition are materials having high adhesion strength to metal materials and resin materials and excellent adhesion. Therefore, the resin composition and adhesive of the present invention are suitable for use in sealing materials and sealing materials in the electric / electronic field and automobile field, or for bonding different materials (metal / resin). Further, the resin composition and the adhesive of the present invention can be used with a force S that can be utilized in the packaging field where gas barrier properties are required.

Claims

The scope of the claims

[2] With respect to 100% by mass of the total amount of the saturated polyester resin (A) and the amorphous polyolefin resin (B), the content of the amorphous polyolefin resin (B) is:

The saturated polyester resin composition according to claim 1, wherein the content is 50% by mass.

[3] The saturated polyester resin composition according to claim 1, further comprising a crystalline polyolefin resin (C).

[4] The saturated polyester resin composition according to claim 3, wherein the crystalline polyolefin resin (C) has a crystal heat of fusion of 50 j / g or more.

[5] The saturated polyester resin composition according to claim 3, wherein the heat of fusion of the amorphous polyolefin resin (B) is 10 j / g or less.

[6] The amorphous polyolefin resin (A), the amorphous polyolefin resin (B), and the crystalline polyolefin resin (C) in a total amount of 100% by mass. The saturated polyester resin composition according to claim 3, wherein the content of B) is;! -30 mass%, and the content of the crystalline polyolefin resin (C) is 3-30 mass%.

[7] The saturated polyester resin composition according to claim 3, wherein the ratio of the crystalline polyolefin resin (C) to 100 parts by mass of the amorphous polyolefin resin (B) is 60 to 250 parts by mass.

[8] An adhesive composition comprising the saturated polyester resin composition according to any one of [1] to [7].

[9] A hot-melt adhesive comprising the saturated polyester resin composition according to any one of [1] to [7].