TW200927826A - Saturated polyester resin composition and hot melt adhesive composition - Google Patents

Abstract

Disclosed is a saturated polyester resin composition which is excellent in sealing properties and adhesive strength to metal materials such as copper and aluminum as well as resin materials such as polyethylene terephthalate. This saturated polyester resin composition is particularly improved in adhesive strength at low temperatures. Specifically, the saturated polyester resin composition contains a saturated polyester resin, a crystalline polyolefin resin and a thermoplastic soft acrylic resin. The saturated polyester resin composition may further contain an epoxy resin. The thermoplastic soft acrylic resin preferably has a Shore A hardness of less than 90 and a melt index at 190 DEG C under a load of 2.16 kg of not less than 10 g/10 minutes.

Description

200927826 IX. The present invention relates to a saturated polyester resin composition containing a saturated polyester resin, a crystalline polyolefin resin, and a thermoplastic soft acrylic resin, and by the composition A hot melt adhesive composition supplied. [Prior Art] The saturated polyester resin is excellent in electrical and thermal properties, and is widely used as a 1C card because it has excellent properties such as a plastic material such as a polyester resin or a metal material such as copper or aluminum. A hot-melt adhesive for a wiring bundle such as a laminate of a polyethylene terephthalate resin and a 1C wafer mounting sheet, or a wiring harness for a motor or a motor electronic field. The above 1C card or wiring harness has been popularized in recent years. On the other hand, the requirement for the adhesive strength of the hot-melt adhesive to be used is high. In particular, maintaining the adhesive strength in a wide temperature range has been a problem in maintaining the peeling strength of the protective film of the IC ® card in a practical temperature range such as winter or summer. Therefore, there has been proposed a hot-melt adhesive composition in which various resin components are added and mixed to a saturated polyester resin. For example, it has been proposed to add a low-density polyethylene resin or a high-density polyethylene resin to a saturated polyester resin and to add an epoxy resin-saturated polyester-based hot-melt adhesive composition (refer to Patent Document 1). Further, a saturated polyester-based hot-melt adhesive composition in which a phenol resin is added to a saturated polyester resin has been proposed (see Patent Document 2). Further, a saturated polyester-based hot-melt adhesive composition comprising a crystalline polyester resin and an amorphous polyester resin and an epoxy resin is known (patent document -4-200927826 3). [Patent Document 1] JP-A-2003-269940 (Patent Document 3) JP-A-2002-1-380269 According to the methods described in Patent Document 1, Patent Document 2, and Patent Document 3, the peel strength with the adhesive is improved by the saturated polyester resin monomer having the main component. However, the peeling of the low-temperature adhesive interface failed to be solved, and the reliability of the practical temperature (-10 ° c to 80 ° C) was poor. An object of the present invention is to provide a resin material such as a metal material such as copper or aluminum or polyethylene terephthalate by improving the composition of a saturated polyester resin composition, at a low temperature (-1 (TC) The composition of the adhesive strength is improved. [Means for Solving the Problem] The present inventors conducted a review of the patents in view of the above problems, and as a result, it was found that a crystalline polyolefin resin was blended in a saturated polyester resin. The thermoplastic soft acrylic resin can improve the adhesive strength in a wide temperature range (-1 0 ° c to 8 ° C), and finally the present invention is completed. The present invention is as follows. 1. A saturated polyester resin composition, It is characterized by containing (A) a saturated polyester resin, (B) a crystalline polyolefin resin, and (C) a thermoplastic-5-200927826 soft acrylic resin. 2. The saturated polyester resin according to the above 1 The composition wherein the thermoplastic soft acrylic resin (C) has a Shore A hardness of less than 9 Å, and a melt index 値 of a temperature of 190 ° C and a load of 21.2 N is 10 g / 1 〇 min • or more. Saturated polyester as described in 2 above In the resin composition, the thermoplastic soft acrylic resin (C) has a hardness of from 1 to 80. φ. The saturated polyester resin composition according to the above 2, wherein the thermoplastic soft acrylic resin (C) The melt-index 値 of the temperature of 190 ° C and a load of 21.2 N is 10 to 1 g / 10 min. The saturated polyester-based resin composition according to the above 1, wherein the thermoplastic soft acrylic resin (C) 6. The saturated polyester resin composition according to the above 5, wherein the thermoplastic soft acrylic resin (C) has a Shore A hardness of less than 90, a temperature of 190 ° C and a load of 21.2 N. The saturated polyester resin composition according to the above 1, wherein the saturated polyester resin (A), the crystalline polyolefin resin (B), and the thermoplastic are the same. When the total amount of the soft acrylic resin (C) is 100% by mass, the content of the thermoplastic soft acrylic resin (C) is from 0.5 to 30% by mass. 8. The saturated polyester resin composition according to the above 1, wherein Contains (D) ring 9. The saturated polyester resin composition according to the above 8, wherein the content of the above 6 - 200927826 crystalline polyaniline resin (B), C) and the epoxy resin (D) oxygen resin (D) is 1 to , which is characterized by containing the above-mentioned one-piece, which is characterized in that the above-mentioned eight-pack composition is used as a hot-melt adhesive assembly property, and the wide temperature range for the high temperature of the resin material such as copper or ethylene vinegar is increased. The interface between the adhesive and the adhesive material peels off the adhesive member. When the total of the saturated polyester resin (A) and the above-mentioned thermoplastic soft acrylic resin is 100% by mass, the above-mentioned ring is 25 mass%. A saturated polyester resin composition comprising a hot melt adhesive composition. 1 1. A composition of a hot-melt adhesive composition Q-supported saturated polyester resin. [Effects of the Invention] The adhesive member of the saturated polyester-based resin of the present invention is improved in strength by a metal material such as aluminum or polyparaphenylene. In particular, the adhesion strength from low temperatures and the damage morphology are improved. Since the state of the detachment is improved, the sealing property is excellent. [Embodiment] [Best Mode for Carrying Out the Invention] An embodiment of the present invention will be described. In the present specification, "acryloyl methacrylate and methacryl fluorenyl group," acrylate and methacrylate. The saturated polyester resin of the present invention is as follows, but the present invention is not affected by (meth) acrylonitrile. Meaning "C methyl) acrylate" means

The product is characterized by comprising: (A 200927826) a saturated polyester resin (hereinafter also referred to as "resin component (A)"), and (B) a crystalline polyolefin resin (hereinafter also referred to as "resin component (B)" And (C) a thermoplastic soft acrylic resin (hereinafter also referred to as "resin component (C)"). The resin component (A) is not particularly limited, and a saturated polyester resin obtained by condensation polymerization of an acid component and a polyol component can be used. The monomer forming the resin component (A), that is, the acid component and the polyol hydrazine component, is not particularly limited, and the following components can be used. Examples of the acid component include an aromatic dibasic acid, an aliphatic dibasic acid, and an alicyclic dibasic acid. Specific examples of the aromatic dibasic acid include terephthalic acid, isophthalic acid, phthalic anhydride, α-naphthalene dicarboxylic acid, P-naphthalene dicarboxylic acid, and ester formations thereof. Specific examples of the aliphatic dibasic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, undecylenic acid, and dodecane. Diacid, its ester forming body, and the like. Further, specific examples of the alicyclic dibasic acid include 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. These acid components may be used alone or in combination of two or more. Among the above-mentioned acid components, the content ratio of terephthalic acid and its ester-forming body 'terephthalic acid is preferably 30 mol from the viewpoint of adhesion strength, and is preferably 30 mol based on the total acid component. %the above. When the terephthalic acid component is 30% by mole or more, sufficient resin cohesive force or hardness can be obtained to improve the adhesive strength, and it is preferable. * 8 - 200927826 Further, as the acid component, maleic acid, gastric acid, dimer acid, etc. may be used insofar as the gelation or adhesive strength of the saturated polyester resin (A) is not impaired. A polyvalent carboxylic acid such as an unsaturated acid, trimellitic acid or pyromellitic acid can be used in a range of 5 mol% or less based on the total acid component. Examples of the polyol component include a glycol such as an aliphatic diol or an alicyclic diol, and a polyhydric alcohol. Among the above-mentioned diols, specific examples of the aliphatic diol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, hydrazine, and 4-butylene. Alcohol, 1,5-pentanediol, 1,6-hexanediol, hydrazine, 8-octanediol, hydrazine, 9-decanediol, neopentyl glycol, 3-methylpentanediol, 2,2 , 3-trimethylpentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and the like. Specific examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. These diols may be used alone or in combination of two or more. © As the above-mentioned diol, it is preferred to use iota, 4-butanediol, hydrazine, and 4-butanediol for a ratio of all polyol components of preferably 3 〇 mol% or more. When 1,4 _ butanol is 30% by mole or more, sufficient cohesive force is obtained and the adhesive strength is improved, so that high heat resistance is obtained. Further, examples of the polyhydric alcohol include glycerin, trimethylolethane, trimethylpropane, and pentaerythritol. These may be used alone or in combination of two or more. The above polyol may be used in a range of 5 mol% or less based on the total polyol component. The melting point of the saturated polyester resin (A) of the present invention is expressed by the differential endothermic peak temperature of IJ/g or more, measured by differential scanning heat-9-200927826 (hereinafter also referred to as "DSC"), and the melting point of g. A polyester resin having a polyester tree of 150 ° C at 50 ° C to 200 ° C is preferred. If the melting point is at 50 ° C ~ 'cloth temperature or adhesion temperature is the appropriate temperature, 'thermal deterioration or oxidation, so excellent adhesion is obtained. The saturated polyester resin (A) is melted and viscous! The melt index 値 )") measured under the condition of a weight of 2 1 · 2 Torr is preferably 10 to 500 g/10 minutes. This 300 g / 10 min, more preferably 1 〇 ~ 1 gram / 10 resin (Α) ΜΙ値 if 10 ~ 500 g / 10 resin components are easy to mix, can get better performance. The above saturated polyester resin (Α) can be produced by •. For example, there are a melt polymerization method in which a raw material and a catalyst are introduced, a temperature at which the temperature is heated, a solid phase polymerization method in which a polymerization is carried out, or a solution using a solvent, but in order to obtain a polyester according to the present invention. And, in terms of economy, it is preferably produced by a transesterification method or a direct esterification method. The content of the resin (A) of the saturated polyester resin composition of the present invention is 9.8 mass%, more preferably 5 0%, based on the total amount of the resin wipe (B) and the resin component (C). 9.5 mass%, the specific heat of fusion is indicated by the melting heat peak temperature, and more preferably in the range of 60 ° C to 2 〇〇 ° C, the adhesion is less likely to occur.荬 At a temperature of 1 90 ° C, the charge (hereinafter also referred to as "MI MI 値 is preferably 1 〇 ~ minutes. This saturated polyester minutes, can be combined with other adhesive strength resin group method to synthesize in the product The melting point may be a polymerization method or the like below the melting point of the product, and may be appropriately polymerized into a melt polymerization method for the purpose, and the above saturated polyester = sub-(A), resin, preferably 40 to preferably 60 to 90% by mass -10-200927826 When the ratio of the resin component (A) is in the range of 40 to 98.5% by mass, sufficient peeling strength can be obtained.

Further, the saturated polyester resin composition of the present invention contains a crystalline polyolefin resin (B). The above resin component (B) serves as a task for preventing concentration stress on the adhesive substrate interface. The resin component (B) is in a state of being dispersed in the form of fine particles in the adhesive composition. The wettability of the surface of the dispersed particles and the saturated polyester resin (A) of the main component is low. Further, since it has a higher modulus of elasticity than the saturated polyester resin (A) of the main component due to crystallization, the peeling stress associated with the adhesive member can be dispersed in the saturated polyester resin (A) and the crystalline polyolefin resin ( B) The interface of dispersed particles. As a result, the concentration of the peeling force at the interface between the adhesive and the adhesive substrate can be prevented, and the peeling adhesive strength becomes high. The degree of crystallization of the resin component (B) is preferably 50 J/g or more at the time of DSC measurement, and the crystallization heat is preferably 50 J/g or more. In particular, the heat of fusion is more preferably 80 J/g or more, and the heat of crystallization is more preferably 80 J/g or more (generally 220 J/g or less). Namely, the heat of fusion or the heat of crystallization of the resin component (B) may be 50 to 220 J/g, and may be 80 J/g to 220 J/g of the above lower limit. When the heat of fusion or the heat of crystallization is in the range of 50 to 22 OJ/g, the difference in the elastic modulus between the resin component (A) and the resin component (B) becomes large, and the peeling stress is dispersed. As a result, the concentration of the peeling stress at the interface between the adhesive and the adhesive substrate can be prevented, and the peeling adhesive strength becomes high. The component forming the resin component (B) is selected from one or more kinds of vinyl monomers having an unsaturated double bond. For example, 'ethylene, propylene-11 - 200927826, and an olefin-based vinyl monomer having 2 to 20 carbon atoms. The resin component (B) is preferably a high-density polyethylene resin containing ethylene as a main component and a low-density polyethylene resin, more preferably a low-density polyethylene having a density of 0.910 to 0.925 g/cm3. The MI 値 when the melt viscosity of the resin component (B) is measured under the conditions of a temperature of 190 ° C and a load of 2 1.2 N is preferably 0.5 to 150 g/10 minutes, more preferably 1 to 120 g/10 minutes. When MI値 is in the range of 0.5 to 150 g/10 Q minutes, the above resin components (A) and (C) can be uniformly mixed to obtain a stable adhesive strength. Further, since the resin composition has moderate flexibility, sufficient adhesive strength can be obtained even at a low temperature. In the resin composition of the present invention, the content of the crystalline polyolefin-based resin (B) is preferably in terms of the total amount of the resin component (A), the resin component (B) and the resin component (C). It is 1 to 30% by mass, more preferably 3 to 25% by mass. When the resin component (B) is in the range of 1 to 30% by mass, the adhesion from the low temperature to the high temperature, which is the subject of the present invention, is improved. The thermoplastic soft acrylic resin (C) has a function of improving adhesion to a resin substrate such as polyethylene terephthalate or a metal substrate such as copper, and particularly low-temperature adhesion strength. As a means of improving the adhesion to the adhesive substrate, the improvement of the wetting of the adhesive substrate by the adhesive is important. Further, it is also important to prevent the concentration of the peeling stress on the interface between the adhesive and the adhesive substrate by the flexibility of the adhesive composition. Since the thermoplastic soft acrylic resin (C) has high flexibility even at room temperature, it is possible to prevent stress concentration at the interface between the adhesive and the adhesive substrate with respect to the peeling stress. -12- 200927826 The above resin component (C) is characterized by a soft resin having high flexibility. Here, the soft system means that the hardness of the ear A specified by ns K62 5 3 is less than 90. The resin component (C) has a hardness of less than 90, preferably 10 to 80, more preferably 30 to 70. When the hardness of the ear A is 90 or more, stress concentration occurs at the interface between the adhesive and the adhesive substrate, and the peeling adhesive strength is lowered. Further, the melt viscosity of the resin component (C) is preferably a melt viscosity close to the resin component (A). The MI 値 of the above resin component (C) is preferably 10 g/10 min or more, and more preferably 丨5 〜; 克 / 1 () minutes' is more preferably 20 to 70 g/10 minutes. When the MI値 is less than 10 g/10 minutes, the difference in the melt viscosity of the resin component (A) is large, and the dispersion of the resin component (C) is poor, and the composition cannot be produced. The main monomer component (meth) acrylate which forms the above resin component (C) is, for example, methyl (meth) acrylate, (meth) acrylate, vinegar or butyl (meth) acrylate. One or more selected from the group consisting of an alkyl alcohol component having a carbon number of 1 to 20 and an esterified monomer group of a (meth)acrylic acid component are selected. Preferably, methyl methacrylate or butyl acrylate is used as a main component. Further, in the range which does not impair the object of the present invention, an aromatic vinyl monomer such as styrene or α-methylstyrene such as ethylene or propylene, or phthalic anhydride can be used. A carboxyl group-containing monomer such as acrylic acid or an epoxy group-containing monomer such as (meth)acrylic acid glycidyl ester. The resin component (C) must have a resin strength (e.g., tensile strength, etc.) and flexibility in the use temperature range. Therefore, it is preferably a block copolymer composed of a hard segment having a rigidity of -13 to 200927826 and a soft segment having flexibility. The hard segment of the block copolymer has the task of maintaining the strength of the resin in the usual temperature range of use, and the soft segment has the task of imparting softness. When the resin component (C) is a random copolymer, the balance between the strength and the flexibility of the resin in the temperature range is deteriorated, the strength of the adhesive itself is lowered, and the peel adhesion strength is lowered. In the method of producing the block copolymer of the above resin component (C), e can be used in any polymerization method. For example, the production methods described in JP-A-2000-4463, JP-A-200-145, No. JP-A No. 2003-275, and JP-A-2004-2844 can be used. In the saturated polyester resin composition of the present invention, the content of the thermoplastic soft acrylic resin (C) is based on the total amount of the resin component (A), the resin component (B), and the resin component (C). It is preferably from 0.5 to 30% by mass, particularly preferably from 1 to 25% by mass, more preferably from 1 to 20% by mass. When the resin component (C) is less than 0.5% by mass, the adhesion strength in a wide range of temperatures from a low temperature to a high temperature cannot be attained. On the other hand, when it exceeds 30 mass%, the composition itself has a lowered strength and the adhesive strength is also lowered. The saturated polyester resin composition of the present invention may further contain (D) an epoxy resin (hereinafter also referred to as "resin component (D)"). The epoxy resin (D) is used as a tackifier to adjust the heat resistance and the elastic modulus of the saturated polyester resin composition of the present invention, and is effectively used for adjusting the adhesion to the adhesive substrate. As the resin component (D), for example, a bisphenol type epoxy resin, a phenol type epoxy resin, a novolac resin, a cresol novolak type epoxy resin or the like can be used. Preferred is a bisphenol resin. The R&B softening point of the above resin component (D) is preferably 180 °C. Here, the R&B softening point means the resin property of JIS K-6863-1994. In the saturated polyester resin composition of the present invention, the resin component (0 content ' is preferably a total amount of the resin component (A), the resin component (B) component (C), and the resin component (D). The mass % ' is more preferably 2 to 20% by mass. When the resin component (D) is in the range of 1 to 25% by mass, the adhesion to the adhesive substrate can be obtained, and the adhesive strength can be improved. Further, the object of the present invention is not impaired. In the above range, the first agent can be used. For example, an anthraquinone resin type tackifier such as an anthracene resin, a phenol resin, an aromatic modified eucalyptus resin, or a rosin-modified phenol resin musk-modified resin type tackifier A petroleum resin type tackifier such as an aliphatic petroleum resin, an alicyclic resin, or an aromatic petroleum resin is equal to the saturated polyester resin composition of the present invention, and may be used arbitrarily within a range not impairing the purpose. The enthalpy is an adjustment of heat resistance, elastic connectivity, productivity, etc. of the saturated polyester resin composition of the present invention. As the above-mentioned chelating agent, for example, talc, organic surface stone, clay can be used. Heavy calcium carbonate , light calcium carbonate, vermiculite, igneous zinc oxide, magnesium hydroxide, aluminum hydroxide, titanium oxide, glass fiber lacquer type ring-shaped epoxy 50%. ~ specified D), resin 1~25 content Fully dense 2, increase the viscosity of oil, hydrogen, etc., the effective rate of the hair, sticky treatment of the slippery stone, montmorillon-15-200927826 stone type bismuth citrate compound, organically treated montmorillonite, etc. Inorganic compound type sputum agent, carbon fiber machine type compound sputum agent, and the like. The amount of the saponifier used is a saturated polyester-based resin composition 1 〇〇% by mass, hereinafter, preferably 20% by mass or less, more preferably 11 in the range of the saturated polyester-based resin composition of the present invention. The thermal decomposition of the saturated polyester resin composition of the invention of any stabilizer Q can be used for the stabilization of the adhesion performance. As a water repellent for stabilizers such as diimine, phenol is an antioxidant, a thioether antioxidant, and the like. The amount of the stabilizer to be used is preferably 5% by mass or less based on 100% by mass of the saturated polyester resin composition. In the range of the purpose of the saturated polyester-based resin composition of the present invention, any coupling agent can be used. 黏 The adhesion of the saturated polyester-based resin composition of the present invention is used for the adjustment of the moist heat stability. Examples of the amine group-containing decane coupling agent such as an alkyl group-based decane coupling agent oxydecane such as a coupling agent-dimethoxydecane, and an epoxy group-containing decane coupling agent such as 3-trimethoxydecane. An aluminum coupling agent such as an alkoxy aluminum diisopropyl ester such as a vinyl decane coupling agent, or a titanate coupling agent such as a titanate. Such features of the present invention can be suitably used. In the case of the present invention, it is usually 30% by mass or less by mass. In, does not damage the hair. The stabilizer is used for the purpose of inhibiting the hydrolysis, and is effective. For example, a polycarbonate or a phosphorus-based antioxidant can be used, and it is usually 10% by mass or less with respect to the present invention, without impairing the present invention. The coupling agent acts on the surface of the substrate. Effectively, for example, dimethyl, 3-aminopropyltriethoxyglycidylpropyl, vinyltriethoxy decane coupling agent, ethyl isopropyl isopropyl trimethoxide can be used. The amount of the use of the stearin coupling agent in the amount of the further modified agent is preferably 5% by mass or less, preferably 3% by mass or less, based on 100% by mass of the saturated polyester resin composition of the present invention. More preferably, it is 2% by mass or less. In the saturated polyester resin composition of the present invention, any other additives may be used within the range not impairing the object of the present invention. For example, a flame retardant such as a bromine-based flame retardant or a phosphorus-based flame retardant, a UV absorber, a plasticizer, a crystal nucleating agent, or the like can be used. The saturated polyester resin composition of the present invention is obtained by mixing the resin component (A), the resin component (B), the resin component (C), or the like by any method. For example, a single-axis extruder, an intermeshing parallel shaft two-axis extruder, an intermeshing-shaped parallel-axis two-axis extruder, an intermeshing-shaped oblique-axis two-axis extruder, and a non-engagement type Axle extruder, incompletely meshed two-axis extruder, kneading machine-shaped extruder, planetary gear-shaped extruder, transfer-mixing extruder, plunger extruder, drum extruder, etc. An extrusion molding machine or a kneading machine or the like is obtained by mixing the respective raw materials. Further, before the above mixing, the mixing may be prepared using a Hanschel mixer or a rotating drum. Each of the raw material components of the saturated polyester resin composition of the present invention may have any shape or character such as a nine-grain shape, a powder shape, or a liquid form. The form of the saturated polyester resin composition of the present invention can be any form. For example, a shape of a nine-grain shape, a powder form, a sheet, a film, a rod, a solution dissolved in a solvent, or the like can be used. The saturated polyester resin composition of the present invention is excellent in adhesion strength to various metals or plastic materials, and particularly excellent in adhesion, and can be used in various fields. For example, it can be used as an adhesive for parts in the field of electronics and motors, a sealing material, a sealing material, and in the field of packaging, it can be used as an adhesive between a laminated film and a laminated sheet. Further, it is possible to use an adhesive for an interior decorative material in an automobile field, a sealing material for a wiring harness, and the like. The method of using the saturated polyester resin composition of the present invention is not particularly limited, and a hot melt method or the like described later can be employed. The hot-melt adhesive composition of the present invention is characterized by comprising the above-described saturated polyester-based resin composition of the present invention.

The hot-melt adhesive composition of the present invention contains the resin components (A), (B), and (C) 'If necessary, the composition containing the additive and the resin components (A), (B) '(C) and D), if necessary, can be a composition containing an additive. In either case, the hot-melt adhesive composition of the present invention is in a molten state at a temperature of from 60 ° C to 200 ° C, and may be different from each other or the same adhesive material. A method of adhering a material using the hot-melt adhesive composition of the present invention will be described. When the shape of the hot-melt adhesive composition of the present invention is a film shape, the film is present between the adhesive materials at room temperature, and is heated to 60 ° C to 200 ° C while being pressurized as needed. Can stick to both. [Examples] Hereinafter, the present invention will be described in more detail by way of Examples. However, the present invention is not limited by the Examples. (Production of Saturated Polyester Resin) In a four--18-200927826 flask equipped with a stirring device, a nitrogen gas introduction tube, a distillation tube, and a thermometer, 0.6 mol of dimethyl terephthalate and 1.6 mol of 1 were charged. 4-butanediol, 〇·2 molar 1,6-hexanediol and 〇.2χ1 (tetra-n-butyl titanate as a catalyst for Γ2 mol, heated while introducing nitrogen gas, at 130 t: After distilling off methanol at ~200 °C, 0.15 mol of isophthalic acid and 0.25 mol of sebacic acid were added, and the water was distilled off at 200 °C to 240 °C, followed by decompression and cooling at 2,500. The reaction was carried out for 3 hours under a reduced pressure of 1 mmH g at ° C to obtain a saturated polyester resin (A-1). The physical properties of the saturated polyester resin (A-1) were used, and the DSC was heated at a temperature of 10 ° C / min. The melting point measured was 135 Å, and the glass transition point was -18 ° C. According to JIS K 7210, 190. (:, the MI値 under the condition of a load of 21.2 N was 80 g/10 min. Moreover, by N MR Analysis to analyze the monomer composition of the polyester resin, the result is that terephthalic acid / isophthalic acid / azelaic acid / 1,4 - butanediol / 1,6 - hexanediol = 60 / 15 / 25/80/20 〇 (composition 1 (Method for the evaluation of the moldability of the composition) 144 g of a saturated polyester resin (A-1) as a resin component (A) and 280 g of a low-density polyethylene made by a Japanese polyolefin company as a resin component (B) Product name "jrex LD JM910" (density: 0.918g/cm3 'melting heat: 1 12J/g, temperature 19 (TC and load 21.2Ν MI値: 20g/10 minutes 'hereinafter also referred to as "LDPE") And 280 g of the product of the resin component (C), "LA-2140E" ("T-1" as "C-1"), was uniformly mixed in advance, and then put into a 30 mm 2-axis extruder "PCM" manufactured by Ikebukuro Co., Ltd. -30", in 16 (TC melt mixing. The molten resin discharged from the S JS machine in the shape of a strand is cooled and solidified in a water tank, and -19-200927826 is cut into nine shapes by a pelletizer to obtain 1 〇〇. In this case, the discharge state of the strand material was visually confirmed, the discharge amount was stabilized, and the surface of the strand material was also smooth, so that the moldability was judged to be good. Further, the above-mentioned C-1 polymethyl methacrylate was aggregated. Di-block copolymer of butyl acrylate-polymethyl methacrylate. Also, in accordance with JIS 'K6253 When the hardness of C-1 was measured, the result was 32 (measuring temperature: 23 ° C). e (Method for producing composition/copper adhesion test piece) The composition 1 was hot pressed at 180 ° C ( O. IMPa, 30 seconds), a sheet having a thickness of about 100 μm (8 0 to 1 2 0 μηι) was produced. The obtained sheet was cut into a width of 25 mm and a length of 50 mm to prepare an adhesive sheet. The copper plate (material C-1100P, thickness 50 μηι) to which the substrate was adhered was cut into a width of 25 mm and a length of 75 mm. The ❹ adhesive sheet was sandwiched between two copper plates in such a manner that the length of the stretched nip portion became about 25 mm, and hot pressed at 180 ° C, O.IMPa for 30 seconds to prepare a composition 1 / copper test piece. . (Adhesive strength test on copper substrate) Example 1 A tensile tester ("Autograph DSS-500" manufactured by Shimadzu Corporation) was used to fix the composition 1/copper test piece to a T-shape. The tensile strength of the test was measured at a tensile temperature of 5 ° C and a tensile speed of 200 mm / min, and the peel adhesion strength was -20-200927826 1 13N/25 mm. Further, when the composition 1/copper test piece produced under the same conditions was subjected to temperature conditions of 23 ° C, 40 t and 50 ° C, the peel adhesion strengths were 108 N/25 mm, 76 N/25 mm and 50 N/25 mm, respectively. Further, the peeling form was visually confirmed, and as a result, it was a cohesive failure form at a temperature of 40 ° C and 50 ° C. Example 2 制作 A composition was produced in the same manner as the composition 1 except that the product component "LA-2250" (hereinafter also referred to as "C-2") manufactured by Kuraray Co., Ltd. was used as the resin component (C). Object 2. The formability is good. Further, a composition 2/copper test piece was produced under the same conditions as the composition 1 / copper adhesion test piece. Then, the adhesion strength was measured by the same method as in Example 1. As a result, when the test temperature was 5 ° C '23 ° C, 40 ° C and 50 ° C, the peel strength was separately (J was 128 N/25 mm, 96 N/25 mm, 6 9 N/2 5 mm and 44 N/25 mm. The peeling pattern was visually confirmed, and as a result, it was agglomerated and destroyed at a temperature of 40 ° C and 〇 50 ° C. Comparative Example 1 uniformly mixed 1 720 g of a saturated polyester resin (A-m) and 280 as a resin component (B) In the above-mentioned "Jrex LD JM910", the composition 3 was obtained in the same manner as in the composition 1. Further, the moldability was good, and the composition was produced under the same conditions as the composition 1 / copper adhesion test piece. Copper test piece. Then, the adhesion strength was measured by the same method as in Example 1. As a result, at the test temperatures of 5 ° C, 23 ° C, 40 ° C, and 50 ° C, the peeling of -21 -27827826 was respectively 2lN/25mm, 54N/25mm, 47N/25mm, and 29N/2 5mm. Further, the peeling form was visually confirmed, and as a result, it was agglomerated and destroyed at a temperature of 50 ° C. It can be seen that compared with Comparative Example 1, it was carried out. The peeling adhesion strength of Examples 1 and 2 in the temperature range of 5 °C to 50 °C is about 2 to 5 times higher, and the failure mode is also As a result of this, it is understood that when the thermoplastic soft acrylic resin is added to the saturated polyester resin, the adhesion to the copper base material is increased, and the adhesive performance and the sealing performance are improved. (Production Method and Formability Evaluation of ～9) The composition materials were prepared by the composition ratio of the composition described in Table 1, and the compositions 4 to 9 were obtained by the same method as the method for producing the composition 1. The moldability was good. Further, the resin components in Table 1 were as follows.

❹ (1) LDPE is a low-density polyethylene resin (manufactured by Nippon Polyolefin Co., Ltd., trade name "Jrex LD JM91 0"). (2) C-1 A thermoplastic soft acrylic resin (manufactured by Kuraray Co., Ltd., trade name "LA-2140E") was used. The Charulus A hardness (JIS K625 3 ) at a temperature of 23 ° C was 32, and the MI 温度 at a temperature of 190 ° C and a load of 21.2 N was 31 g/10 min. -22- 200927826 (3) C-2 A thermoplastic soft acrylic resin (Kuraray product name "LA-2250") is used. The ternary block copolymer of the C-2 series poly(methyl methacrylate)-polymethyl methacrylate at a temperature of 23 ° C has a Charging A hardness (JIS K6253 ) of 190 ° C and a load of 21.2 N. The MI値 is 25 g/10 min. 〇 (4) C-3 A thermoplastic soft acrylic resin (Kuraray product name "LA-42 8 5") is used. The C-3 series polybutylene methacrylate-polymethyl methacrylate ternary block copolymer has a Charging A hardness (JIS K625 3 ) at a temperature of 23 ° C of 1 90 ° C and a load of 2 The MI値 of 1.2 N is 1.5 g / 10 min. Q (5) Soft acrylic rubber

The product name "Metabren W ' (6) epoxy resin manufactured by Mitsubishi Electric Co., Ltd. was used as a resin component (D) as a resin component (D) at a temperature of 1 3 8 ° C. Examples 3 to 4 and comparison Example 2 Compositions 4 to 6 were used to prepare a composition/copper test piece, a system, a commercial ester-polypropylene 65, a temperature system, a commercial ester-polypropylene 95, and a temperature of -310". . R&B Soft The adhesion strength was measured by the same method as in Example 1 of -23-200927826. The results are shown in Examples 3 to 4 and Comparative Example 2 of Table 2. In the results of the failure mode in Table 2, the "interface" means that the interface between the resin composition and the adhesive substrate is peeled off, and "aggregation" means that the resin composition is agglomerated and destroyed.

-24- 200927826

Composition rH (N inch inch 〇τ^Η stable unevenness, bad Ο CN 〇 〇 unstable can not form ON m 3 Ο Τ"^ Good good 00 oo Cn ο Good good OS VO ο Good-53⁄4 p inch OO IT1 100 Good Oo inch inch^Τ) Ο Τ·"^ Good inch (N inch inch ο good m 00 inch 良好 Good CN CN inch inch ο τ-1 Good and good r*H CN inch inch Ο rH Good good composition saturated polyester resin Al (% by mass LDPE (% by mass) cl (% by mass) C-2 (% by mass) C-3 (% by mass) Soft acrylic rubber (% by mass) Epoxy resin (% by mass) Total (% by mass) Formability strand discharge Stable formability strand surface smoothness-25- 200927826 ο Ρ 沄11 Agglutination agglutination agglutination agglutination agglutination agglutination agglutination peeling adhesion strength (N/25mm) S Ρ ο 11 agglutination agglutination interface agglutination interface agglutination agglutination 晅 peel adhesion strength (N/25mm) (Ν m 00 (N Ρ Destruction interface interface interface interface interface agglutination m 虼 stripping Strength (N/25mm) g 7 ^Η (N 00 1—Η 〇〇Ρ 11 晅晅 Interface interface interface interface target peeling adhesion strength (N/25mm) mr—<r"H 〇〇卜τ- VO VO On sample name composition 1 / copper test piece composition 2 / copper test piece composition 3 / copper test piece composition 4 / copper test piece composition 5 / copper test piece composition 6 / copper test piece composition 7 / copper test piece composition 8 / copper test piece composition 9 / copper test piece test number Example 1 Example 2 Comparative Example 1 Example 3 Example 4 丨 Comparative Example 2 Example 5 Example 6 Example 灏 φ / ι ι - - - - - 比较 姻 姻 姻 姻 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较 比较The peel adhesion strength at a temperature of ° C was slightly higher. Moreover, the peel adhesion strength at a low temperature of 5 ° C was not improved. On the other hand, compared with Comparative Example 1 or Comparative Example 2, It can be seen that in Examples 3 and 4, in the temperature range of 5 ° C to 50 ° C, the peel adhesion strength is several times higher than the height, and Above 40 ° C tend to aggregate failure mode also destructive, adhesion to a copper substrate is high, adhesion properties and high sealing properties. Examples 5 to 7 Using the compositions 7 to 9 to prepare a composition/copper test piece, the measurement of the peel adhesion strength was carried out in the same manner as in Example 1. The results are shown in Examples 5 to 7 of Table 2. In Example 5 and Example 6, although the amount of V used in the resin component (C) was 5% by mass and 3% by mass, respectively, peeling was observed in a wide temperature range of 5 ° C to 50 ° C. Improvement in adhesion strength and damage morphology. (Evaluation of the production and the formability of the composition 1 〇 to 1 1) The acrylic thermoplastic resin C-3 was used as the resin component (C), and the composition shown in Table 1 was the same as the method for producing the composition 1. The operation of the composition 10 was carried out, and as a result, the strand was blocked halfway, and a stable strand could not be obtained, so that the composition could not be produced. Therefore, it is considered that the acrylic tree -27-200927826 which is high in hardness and low in MI is not able to obtain the composition shown in the present invention. Further, in place of the resin component (C), a soft acrylic rubber having no thermoplastic or non-block copolymer was used, and the composition shown in Table i was used to produce a composition by the same operation as the method for producing the composition 1. u, the result visually confirms that there are numerous irregularities on the surface of the strand. Therefore, when a soft acrylic rubber having no thermoplasticity is used, since it is not uniformly dispersed in the resin component (A), for example, when it is supplied as a sheet-like film-like adhesive, defects such as fisheye or sheet breakage occur. The possibility of a situation is great. (Adhesion strength test on polyethylene terephthalate film) Example 8 and Comparative Example 3 In addition to the use of the composition 6 and the composition 4 shown in Table 1 and the thickness of the adhesive substrate ΙΟΟμηι An adhesive test piece was produced by a method similar to G in the case of a copper test piece except for a polyethylene terephthalate film (hereinafter also referred to as "PET film"), and the same stretching as in the method shown in Example 1 was carried out. test. The results are shown in Table 3. In the results of the failure mode in Table 3, the "interface" means that the interface between the resin composition and the adhesive substrate is peeled off, and "aggregation" means that the aggregation of the resin composition is broken, and "material breakage" means the PET film. damage. -28- 200927826 50°C Destructive Form Agglutination Interface Peeling Adhesion Strength (N/25mm) 5 40°C Destruction of Morphological Material Breaking Interface Peeling Adhesion Strength (N/25mm), 23 °C Destruction of Morphological Material Breaking Material Peeling Adhesion Strength ( N/25mm) 1 1 1 1 1 » » . 1 1 1 1 1 1 P in Destructive morphological material broken material peeling adhesion strength (N/25mm) 1 1 1 1 1 1 ! 1 1 1 Coffee 1 1 Sample name :螌Μ: u Yue: Parrot: tender; Η ω > m CL· » CL· Ό i inch Rong: Song Sheng: play test number Example 8 Comparative Example 3 «φ/ιπυΙοο(Ν:Μ·« -}5ϊ 200927826 According to Table 3, the peel adhesion strength of Example 8 over a wide temperature range was stronger than that of Comparative Example 3 using a composition containing no thermoplastic soft acrylic resin and epoxy resin, and PET film was used. It was confirmed that the material destruction was easy. As a result, it was confirmed that the composition containing the thermoplastic soft acrylic resin (C) was compared with the composition containing epoxy resin instead of the thermoplastic soft acrylic resin to polyethylene terephthalate. Excellent adhesion or sealing. e [Industrial use The saturated polyester resin composition of the present invention and the hot-melt adhesive composition using the composition are materials having high adhesion to a metal material or a resin material and excellent adhesion. Therefore, it is suitable for use in Adhesion of sealing materials or closure materials in motors, electronics, and automotive fields, or different materials (metal/resin). 〇-30-

Claims (1)

200927826 X. Patent application scope 1. A saturated polyester resin composition comprising (A) a saturated polyester resin, (B) a crystalline polyolefin resin, and (C) a thermoplastic soft acrylic resin. 2. The saturated polyester resin composition according to claim 1, wherein the thermoplastic soft acrylic resin (C) has a Charging A hardness of less than 90, and a temperature of 19 (rc and a load index of 212 N) It is 10 g / 10 minutes or more. 3_ The saturated polyester resin composition of claim 2, wherein the thermoplastic soft acrylic resin (C) has a hardness of 1 〇 to 8 0 〇 4. The saturated polyester resin composition according to claim 2, wherein the thermoplastic soft acrylic resin (C) has a melt index of 1 〇 1 to 1 / at a temperature of 190 ° C and a load of 21.2 N. 10 minutes. 5. The saturated polyester resin composition according to claim 1 of the patent scope, Ο wherein the thermoplastic soft acrylic resin (C) is a block copolymer. 6. Saturated polymer as in claim 5 The ester-based resin composition, wherein the thermoplastic soft acrylic resin (C) has a Shore A hardness of less than 90, and a melt index 値 of a temperature of 190 ° C and a load of 21.2 N is 10 g / 1 〇 min or more. Saturated polyester resin as claimed in item 1 of the patent application The thermoplastic soft acrylic resin (C) when the total of the saturated polyester resin (A), the crystalline polyolefin resin (B), and the thermoplastic soft acrylic resin (C) is 100% by mass. The content of the compound is 0.5 to 30 -31 - 200927826% by mass. 8. The saturated polyester resin composition of the first application of the patent scope, which further contains (D) an epoxy resin. The saturated polyester resin composition, wherein the saturated polyester resin (A), the crystalline polyolefin resin (B), the thermoplastic soft acrylic resin (C), and the epoxy resin (D) When the total amount is 1% by mass, the content of the epoxy resin (D) is 1 to 25 ❿% by mass. 1 0. A hot-melt adhesive composition characterized by containing the saturation of the first item of the patent application. Polyester resin composition 11. A hot-melt adhesive composition characterized by a saturated polyester resin composition containing the scope of claim 8 ❹ -32- 200927826 VII. Designation of representative drawings: (1) The representative representative of the case is: No (2) The symbol of the representative figure of this representative figure is simple: no 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -3-