Polyester-based resin composition, adhesive composition, adhesive, adhesive sheet, and double-sided adhesive sheet

Abstract

To provide a polyester-based resin composition which uses a raw material derived from a plant that is friendly to global environment, has good adhesive physical property to various adherends, and is excellent in adhesive physical properties such as adhesive force and holding force.SOLUTION: A polyester resin composition contains a polyester-based resin, wherein the polyester-based resin is a polyester-based resin (a1) which includes a structural unit derived from at least one kind of compound (α1) of 44C dimer acids and 44C dimer diol, as a structural unit derived from at least one of polyvalent carboxylic acids (a) and polyol (b), and has a content ratio of the structural unit derived from the compound (α1) of 25 mol% or more with respect to the total of the structural units derived from the polyvalent carboxylic acids (a) and the polyol (b), and a number average molecular weight of 3,000 or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polyester resin composition, a pressure-sensitive adhesive composition, a pressure-sensitive adhesive, a pressure-sensitive adhesive sheet, and a double-sided For more details about the adhesive sheet, please refer to the polyester made from environmentally friendly plant-based materials. A steric resin composition that, when used as an adhesive, has excellent adhesive properties such as adhesive strength and holding power. Polyester resin composition, pressure-sensitive adhesive composition, pressure-sensitive adhesive, pressure-sensitive adhesive sheet and double-sided pressure-sensitive adhesive sheet This is related to the [Background technology]

[0002] In recent years, in order to make products smaller and lighter, adhesives have come to be used to bond parts. Instead of the commonly used acrylic resin, Pressure sensitive adhesives using polyester resins, which have excellent adhesive strength, are also being considered.

[0003] On the other hand, in recent years, as part of measures to combat the depletion of fossil fuel resources and global warming, renewable resources have become increasingly popular. The use of plant-derived raw materials is recommended, and the use of plant-derived raw materials that are environmentally friendly is recommended. There is a demand for adhesives with a high biomass content.

[0004] As an example of a polyester-based adhesive using such plant-derived raw materials, Patent Document 1 discloses Polymerization was performed using dimer acid as the carboxylic acid component and dimer diol as the diol component. The polyester is composed of 1 mole of diol per mole of carboxyl group contained in the dicarboxylic acid component. A polyester having 1.04 to 2.10 moles of hydroxyl groups contained in the polyester component and a tackifier are used. The adhesive contains a small amount of organic solvent, can be applied thickly, and has excellent adhesion, retention, and resistance to cracking. It has been proposed that it has excellent efficiencies.

[0005] Furthermore, in Patent Document 2, dimer acid is used as the dicarboxylic acid component and diol is used as the diol component. Polyester polymerized using imidyl, with even carbon atoms as the polyol component. Polyester-based adhesives composed of several glycols have been proposed. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2014-169419 A [Patent Document 2] International Publication No. 2020 / 218174 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the techniques disclosed in Patent Documents 1 and 2 use dimer acid, but olein It is a 36-carbon fatty acid obtained by dimerization of unsaturated fatty acids with 18 carbon atoms, such as oleic acid and linoleic acid. Only examples using dimer acids are listed, and unsaturated fatty acids with 22 carbon atoms such as erucic acid are not used. There is no description of dimer acids with 44 carbon atoms obtained by dimerization. .

[0008] Generally, when polyester resin is used as an adhesive, it is necessary to use an isocyanate-based Additives such as crosslinking agents, epoxy compounds, metal chelate compounds, and tackifiers are also used. It is often used. However, environmentally friendly plant-derived raw materials, such as dimers with long alkyl chains, When polyester resin compositions are prepared using dimer diols or acids, additives are When added, the adhesiveness sometimes decreased.

[0009] In this invention, therefore, in light of the above background, the use of plant-derived raw materials that are environmentally friendly is Among them, the carbonyl compounds obtained by dimerizing unsaturated fatty acids with 22 carbon atoms, such as erucic acid, At least one of dimer acids having a prime number of 44 and dimer diols having a carbon number of 44 was used. In some cases, it has good adhesive properties for various adherends and has excellent adhesive properties such as adhesive strength and holding power. Polyester resin composition, pressure-sensitive adhesive composition, pressure-sensitive adhesive, pressure-sensitive adhesive sheet, and double-sided pressure-sensitive adhesive sheet The purpose is to provide. [Means for solving the problem]

[0010] However, the present inventors have found that in a polyester resin composition containing a polyester resin, The polyester resin is preferably a polyester resin having a polyvalent carboxylic acid and a and polyols, dimer acids having 44 carbon atoms and dimer diols having 44 carbon atoms. At least one compound-derived structural unit is a polycarboxylic acid-derived structure and a polyol-derived structure. By containing 25 mol % or more of the total units and making the number average molecular weight 3000 or more, The present invention has been completed based on the discovery that the above problems can be solved by the above method.

[0011] The present inventors also found that, in a pressure-sensitive adhesive composition containing a polyester resin, The ester resin is a polycarboxylic acid and a polyol that constitute the polyester resin. At least one compound selected from the group consisting of dimer acids having 44 carbon atoms and dimer diols having 44 carbon atoms. It has been found that the above problems can be solved by incorporating a structural unit derived from a compound, and was completed.

[0012] That is, the present invention has the following aspects [1] to

[10] . [1] A polyester-based resin composition containing a polyester-based resin, The polyester resin is a structural unit derived from a polyvalent carboxylic acid (a) and a polyol (b). unit, and derived from at least one of the polyvalent carboxylic acids (a) and the polyol (b). As the structural unit of the compound, a small amount of dimer acids having 44 carbon atoms and dimer diols having 44 carbon atoms are used. At least one structural unit derived from the compound (α1), and the content ratio of structural units derived from at least one compound (α1) in the dimer diol is 25 mol % or more of the total of structural units derived from polyvalent carboxylic acids (a) and polyol (b) The polyester resin (A1) is a polyester having a number average molecular weight of 3,000 or more. Stellate resin composition. [2] The weight average molecular weight of the polyester resin (A1) is 10,000 or more. 2. The polyester resin composition according to claim 1 . [3] The polyester resin composition has a biomass content of 50% or more. [1] Or The polyester resin composition according to [2]. [4] Any of [1] to [3] further containing a polyisocyanate compound (B). The polyester resin composition according to any one of claims 1 to 5. [5] The polymerizable composition according to any one of [1] to [4], further comprising a hydrolysis inhibitor (C). Polyester resin composition. [6] A pressure-sensitive adhesive composition containing a polyester resin, The polyester resin is a structural unit derived from a polyvalent carboxylic acid (a) and a polyol (b). unit, and derived from at least one of the polyvalent carboxylic acids (a) and the polyol (b). As the structural unit of the compound, a small amount of dimer acids having 44 carbon atoms and dimer diols having 44 carbon atoms are used. A polyester resin (A) containing structural units derived from at least one compound (α1). The pressure-sensitive adhesive composition. [7] The pressure-sensitive adhesive composition according to [6], having an adhesive strength of 7 N / 25 mm or more under the following conditions: Adhesive strength: When an adhesive layer made of the adhesive composition is formed on a substrate to form an adhesive sheet, the adhesive strength is After attaching it to a polypropylene plate and leaving it for 30 minutes at 23°C and 50% RH, , 180 degree peel strength (N / 25mm) from the substrate at a peel speed of 300mm / min. [8] A pressure-sensitive adhesive obtained by crosslinking the pressure-sensitive adhesive composition according to [6] or [7]. [9] An adhesive sheet having an adhesive layer containing the adhesive described in [8].

[10] A double-sided pressure-sensitive adhesive sheet having an adhesive layer containing the pressure-sensitive adhesive described in [8]. Effect of the Invention

[0013] The polyester resin composition of the present invention is a polyester resin having a high biomass content and is environmentally friendly. Although it is a steric resin composition, when used as an adhesive, it has good adhesive properties for various adherends. It is also good in retention. Therefore, the polyester resin composition of the present invention is suitable for use in laminating optical members. Single-sided or double-sided adhesive sheets, single-sided or double-sided adhesive sheets for fixing components of portable electronic devices, single-sided or double-sided adhesive sheets for fixing electronic components It is effectively used for double-sided adhesive sheets, etc.

[0014] In addition, the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition having a high biomass content and being environmentally friendly. However, when used as an adhesive, it has good adhesive properties for various substrates and excellent holding power. do. Therefore, the pressure-sensitive adhesive composition of the present invention is suitable for use in laminating optical members on one or both sides. Surface adhesive sheets, single-sided or double-sided adhesive sheets for fixing components of portable electronic devices, and electronic components It can be effectively used in such applications. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Hereinafter, a polyester resin composition according to one embodiment of the present invention (hereinafter, "the present polyester resin composition") will be described. The adhesive composition according to one embodiment of the present invention (hereinafter referred to as the "adhesive composition") The composition of the adhesive composition will be described in detail, but these are only examples of preferred embodiments. This shows that. In the present invention, the term "carboxylic acids" includes not only carboxylic acids but also carboxylic acids Carboxylic acid derivatives such as salts, carboxylic acid anhydrides, carboxylic acid halides, and carboxylic acid esters It also includes conductors.

[0016] The polyester resin composition contains a polyester resin, The fat is at least one of a dimer acid having 44 carbon atoms and a dimer diol having 44 carbon atoms. The structural unit derived from the compound (α1) is converted into a structural unit derived from polyvalent carboxylic acids (a) and polyols (b). A polyester having a number average molecular weight of 3,000 or more and a content of 25 mol % or more of the total structural units. It is a steric resin (A1). The adhesive composition contains a polyester resin, and the polyester resin is As a structural unit derived from at least one of the polyvalent carboxylic acid (a) and the polyol (b), At least one compound of a dimer acid having 44 carbon atoms and a dimer diol having 44 carbon atoms The polyester resin (A) contains a structural unit derived from the compound (α1). The polyester resin (A) will be described in detail below.

[0017] <Polyester resin (A)> The polyester resin has a resin structure that includes structural units derived from polyvalent carboxylic acids and It has a structural unit derived from a polyol, and is usually a polyvalent carboxylic acid and a polyol. The polymerizable composition can be obtained by polymerizing a polymerization component containing the following:

[0018] The polyester resin (A1) used in the polyester resin composition is a polyvalent carbo (a) a dimer acid having 44 carbon atoms and (b) a polyol having 44 carbon atoms. At least one compound (α1) of the dimer diol (hereinafter referred to as "compound (α1)") The content of the structural unit derived from the compound (α1) is 25 mol % or more of the total of structural units derived from polyvalent carboxylic acids (a) and polyol (b) and the number average molecular weight is 3000 or more.

[0019] The polyester resin (A) used in the pressure-sensitive adhesive composition is a polyvalent carboxylic acid ( As a structural unit derived from at least one of the polyol (a) and the polyol (b), It contains the following structural units.

[0020] [Compound (α1)] At least one of the above dimer acids having 44 carbon atoms and dimer diols having 44 carbon atoms As described above, the compound (α1) is a polyvalent carboxylic acid, a dimer acid having 44 carbon atoms. and at least one of a dimer diol having 44 carbon atoms, which is a polyol.

[0021] [Dimer acids with carbon number of 44] The dimer acids with 44 carbon atoms are mainly composed of unsaturated fatty acid dimers with an average of 22 carbon atoms. The dicarboxylic acids having 44 carbon atoms are the above-mentioned unsaturated fatty acid dimers having an average of 22 carbon atoms. Examples of fatty acids that are primarily derived from the body include unsaturated fatty acids such as erucic acid. In this case, the term "main component" refers to a component whose content is 90% by weight or more of the total, preferably This refers to a component that is 95% by weight or more, and more preferably 98% by weight or more.

[0022] The dimer acids having 44 carbon atoms are derived from unsaturated fatty acids such as erucic acids. and hydrogenated products of the above dimer acids. Of these, hydrogenated products are preferred because they are easy to prevent crystallization. I wish.

[0023] The raw materials for the above-mentioned dimer acids having 44 carbon atoms are usually plants, beef tallow, etc. In the present day, any dimer acid with 44 carbon atoms derived from any source can be used. It is preferable to use environmentally friendly plant-derived raw materials. This makes it possible to increase the biomass content of the polyester resin (A) described below.

[0024] The above-mentioned dimer acids having 44 carbon atoms are used as copolymerization components of the polyester resin (A). In the case where the polyvalent carboxylic acid (a) is used, the content is 25 to 100 mol % based on the total polyvalent carboxylic acid (a). is preferable, particularly preferably 30 to 99 mol %, further preferably 40 to 90 mol %, and especially preferably If the content is too low, the composition becomes too hard and sticky. If the content is too high, the material becomes too soft and has a tendency to become slightly brittle. The adhesive properties tend to decrease.

[0025] [Dimer diol with 44 carbon atoms] The dimer diol having 44 carbon atoms used in the polyester resin (A) is generally The diol is derived from the above-mentioned dimer acid having 44 carbon atoms. Merdiol is a plant-derived raw material, just like dimer acids with 44 carbon atoms. is preferred.

[0026] The above-mentioned dimer diol having 44 carbon atoms is used as a copolymerization component of the polyester resin (A). When used, the content is 25 to 100 mol % based on the total polyol (b). Preferably, the content is 30 to 99 mol %, more preferably 40 to 80 mol %, and especially preferably The content is preferably 50 to 80 mol %. If the content is too low, the adhesive properties are reduced. However, if the content is too high, the adhesive becomes too soft and the adhesive properties are somewhat reduced. There is a tendency for

[0027] [Aromatic compounds] The polyester resin (A) may contain an aromatic compound as a copolymerization component. Examples of the aromatic compounds include aromatic polyvalent carboxylic acids and aromatic polyols. In view of their excellent adhesive strength and holding power, aromatic polyvalent carboxylic acids are used as aromatic compounds. It is preferable to use

[0028] (Aromatic polycarboxylic acids) The aromatic polyvalent carboxylic acids include divalent aromatic dicarboxylic acids, trivalent or higher aromatic The aromatic polyvalent carboxylic acids are preferred because they can stably produce the polyester resin (A). Aromatic dicarboxylic acids are preferably used.

[0029] Examples of the aromatic dicarboxylic acids include phthalic acids, terephthalic acids, isophthalic acids, benzylmalonic acids, diphenic acids, 4,4'-oxydibenzoic acids, 1,8- Naphthalenedicarboxylic acids, 2,3-naphthalenedicarboxylic acids, 2,7-naphthalenedicarboxylic acids Carboxylic acids, such as naphthalenedicarboxylic acids and other aromatic dicarboxylic acids of the benzene series; thiophenedicarboxylic acids, thiophenedicarboxylic acids (pyrrole, pyrazole, imidazole, Examples of the heterocyclic dicarboxylic acids include pyridine, pyridazine, pyrimidine, pyrazine, etc. These may be used alone or in combination of two or more. Therefore, terephthalic acids, isophthalic acids, and furandicarboxylic acids are preferred.

[0030] Examples of the aromatic polyvalent carboxylic acids having a valence of three or more include trimellitic acids, pyrrolic acids, These may be used alone or in combination of two or more. It may be used.

[0031] In addition, polyethylene terephthalate is used as the aromatic polycarboxylic acid. The polyethylene terephthalate is preferably a mixture of terephthalic acid and ethylene glycol. The polyester resin is a polymerized polyester resin. Therefore, the polyester resin (A) contains polyethylene as a structural unit derived from an aromatic compound. The terephthalate-derived polymer has structural units derived from terephthalic acids. The polyethylene terephthalate may be optionally mixed with isophthalic acids, phthalic anhydrides, etc. , adipic acids, cyclohexanedicarboxylic acids, sebacic acids, 1,3-butanediol Modified with substances such as cyclohexanedimethanol, 1,4-butanediol, etc. The polyethylene terephthalate may be a virgin product. Although recycled products may be used, the use of recycled products is preferable from the viewpoint of the global environment.

[0032] The above aromatic polyvalent carboxylic acids are used as the copolymerization components of the polyester resin (A). In this case, the content is 1 mol % or more and less than 50 mol % based on the total polyvalent carboxylic acids (a). It is preferable that the content of the amine is 5 to 47 mol %, more preferably 10 to 43 mol %. %, particularly preferably 15 to 40 mol %, and more preferably 20 to 36 mol %. If the content is too low, the cohesive strength will decrease, resulting in a decrease in adhesive strength and making it difficult to obtain sufficient adhesive performance. If there is too much, the initial adhesive strength (tack) tends to decrease.

[0033] (Aromatic polyol) The aromatic polyol includes a divalent aromatic diol. Examples of the divalent aromatic diol include bisphenol A, 4,4'-thiodiphenyl ether, and 1,2-diphenyl ether. phenol, 4,4'-methylenediphenol, 4,4'-dihydroxybiphenyl, o- , m-, and p-dihydroxybenzene, 2,5-naphthalenediol, and p-xylene Diols and their ethylene oxide adducts and propylene oxide adducts. These may be used alone or in combination of two or more.

[0034] When the aromatic polyol is used as a copolymerization component of the polyester resin (A), The content is preferably 1 to 50 mol % based on the total polyol (b), and more preferably The content is preferably 5 to 40 mol %, and more preferably 10 to 30 mol %. If it is too little, the cohesive strength will decrease and adhesive strength will tend to decrease, and if it is too much, the initial adhesive strength will decrease. There is a tendency for

[0035] The polyester resin (A) used in the present polyester resin composition is the above compound ( α1) Besides the aromatic compounds, aliphatic compounds may be used as copolymerization components.

[0036] [Aliphatic compounds] Examples of the aliphatic compound include aliphatic polycarboxylic acids and aliphatic polyols. .

[0037] (Aliphatic polycarboxylic acids) The aliphatic polyvalent carboxylic acids include divalent aliphatic dicarboxylic acids, trivalent or higher polyvalent Examples include carboxylic acids. Examples of the aliphatic dicarboxylic acids include malonic acids, dimethylmalonic acids, succinic acids, and the like. Acids, glutaric acids, adipic acids, trimethyladipic acids, pimelic acids, 2,2 -Dimethylglutaric acids, azelaic acids, sebacic acids, 1,9-nonanedicarboxylic acid linear alkyl dicarboxylic acids such as decane dicarboxylic acids, fumaric acids, maleic acyclic aliphatic dicarboxylic acids such as itaconic acids, thiodipropionic acids, and diglycolic acids carboxylic acids; 1,3-Cyclopentanedicarboxylic acids, 1,2-Cyclohexanedicarboxylic acids, 1 ,4-Cyclohexanedicarboxylic acids, 2,5-Norbornanedicarboxylic acids, Adamantan Examples of the dicarboxylic acid include cyclic aliphatic dicarboxylic acids such as benzenedicarboxylic acids. Examples of the trivalent or higher polyvalent carboxylic acids include adamantane tricarboxylic acid. Acids and the like can be mentioned. These aliphatic polyvalent carboxylic acids may be used alone or in combination of two or more kinds.

[0038] As the aliphatic polyvalent carboxylic acids, from the viewpoint of improving the initial adhesive strength (tackiness), Contains acyclic aliphatic dicarboxylic acids with 4 or more carbon atoms (including the carbon of the carboxy group). Among them, azelaic acids, sebacic acids, etc., having a carbon number (carbon number of the carboxy group) are preferable. It is more preferable that the compound contains 9 to 12 acyclic aliphatic dicarboxylic acids (including the above).

[0039] As a copolymerization component of the polyester resin (A), the above-mentioned acyclic aliphatic diamine having 4 or more carbon atoms is used. When polycarboxylic acids are used, the content is 95 mol% based on the total polycarboxylic acids (a). It is preferable that the content is 5 to 90 mol %, and more preferable that the content is 10 to 70 mol %. If the content is too high, the adhesive strength may decrease or the resin may crystallize and become insufficient. As a result, satisfactory adhesive performance tends to be lost.

[0040] In addition, the above-mentioned aliphatic polycarboxylic acids are preferably made of plant-derived fats and oils in order to increase the biomass content. It is preferable to use aromatic polyvalent carboxylic acids. Examples of the plant-derived aliphatic polycarboxylic acids include sebacic acid derived from castor oil. and succinic acids derived from corn.

[0041] (Aliphatic polyol) The aliphatic polyol may be a dihydric aliphatic diol, a trihydric or higher aliphatic polyhydric alcohol, or Examples include Examples of the divalent aliphatic diol include ethylene glycol, diethylene glycol, ethanol, triethylene glycol, propylene glycol, dipropylene glycol, 1, 3-Propanediol, 2,4-Dimethyl-2-ethylhexane-1,3-diol, 2 -Methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol ( Neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2- Ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4 -Butanediol, 1,5-Pentanediol, 1,6-Hexanediol, 3-Methyl -1,5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, etc. Acyclic aliphatic diols; 1,2-Cyclohexanedimethanol, 1,3-Cyclohexanedimethanol, 1,4 -Cyclohexanedimethanol, Spiroglycol, Tricyclodecanedimethanol, A Damantanediol, Isosorbide, 2,2,4,4-Tetramethyl-1,3-cyclo butanediol and other cyclic aliphatic diols. Examples of the trihydric or higher aliphatic polyhydric alcohol include pentaerythritol, diphenyl ether, Pentaerythritol, Tripentaerythritol, Glycerin, Trimethylolpropane , Trimethylolethane, 1,2,4-Butanetriol, 1,2,5-Pentanetriol Examples of the tert-butyl ether include 1,3,6-hexanetriol, 1,3,6-hexanetriol, and adamantanetriol. These aliphatic polyols may be used alone or in combination of two or more kinds.

[0042] Among these, the glass transition temperature (Tg) of the polyester resin (A) is lowered, and the initial In order to improve adhesion, a linear acyclic aliphatic diol is added to the polyol. It is preferable that the diol is a linear acyclic aliphatic diol having 2 to 18 carbon atoms. Particularly preferred are ethylene glycol, diethylene glycol, and 1,3-propane glycol. Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol In particular, lowering the glass transition temperature (Tg) of the polyester resin (A) is Ethylene glycol is particularly preferred since it can provide superior adhesion.

[0043] As a copolymerization component of the polyester resin (A), the above-mentioned linear acyclic aliphatic diol When used, the content is 1 to 100 mol % based on the total polyol (b). is preferred, more preferably 20 to 90 mol %, further preferably 40 to 80 mol %, and particularly If the content is too low, stable resin formation is not possible. tends to be difficult to obtain.

[0044] The above aliphatic polyol is a plant-derived polyol in order to increase the biomass content. It is preferable that Examples of the plant-derived polyol include isosorbide and polyols derived from castor oil. Fatty acid ester diols, bio-ethylene glycol, and bio-1,3-propane glycol Licor, biobutylene glycol, etc. Among them, bioethylene glycol Preferred are bio-1,3-propane glycol and bio-1,3-propane glycol.

[0045] As the linear acyclic aliphatic diol, polyethylene terephthalate is preferably used. As described above, polyethylene terephthalate is a polymer made of terephthalic acid and ethylene Polyethylene terephthalate is a polymerized polyester resin. By using the tartrate, the polyester resin (A) is a straight-chain acyclic aliphatic dimer. The structural unit derived from ethylene glycol is polyethylene terephthalate. The polyethylene terephthalate contains the structural unit described above. Although recycled or non-recyclable products may be used, the use of recycled products is preferable from the viewpoint of the global environment. stomach.

[0046] Furthermore, the polyester resin (A) may contain a polyisocyanate compound (B) described later. In order to form reactive sites and increase the cohesive strength, aliphatic polyols having three or more valences are used. It is preferable to use a hydric alcohol, for example, trimethylolpropane, trimethylol Luetane, glycerin, pentaerythritol, 1,2,4-butanetriol, 1,2 ,5-pentanetriol, and 1,2,6-hexanetriol can be used. These may be used alone or in combination of two or more. It is particularly preferable to use trimethylolpropane since this is unlikely to cause oxidation.

[0047] The content of the aliphatic polyhydric alcohol having a valence of three or more relative to the total amount of the polyol (b) is The content is preferably 20 mol % or less, and more preferably 0.1 to 10 mol %. The amount of the trihydric or higher aliphatic polyhydric alcohol is preferably 0.5 to 5 mol %, and particularly preferably 0.5 to 5 mol %. If the content is too high, production of the polyester resin (A) tends to become difficult.

[0048] As described above, it is preferable to use aliphatic polyols derived from plants. In the case where the polyvalent carboxylic acid (a) has a high biomass content, it is preferable to use a plant-derived polycarboxylic acid (a) from the viewpoint of ease of polycondensation. Aliphatic polyols not derived from plants may be used. However, even in this case, it is necessary to increase the biomass content. In order to reduce the amount of the cyclic aliphatic diol, it is preferable to use a linear acyclic aliphatic diol having 4 or less carbon atoms. In particular, it is preferable to use a non-cyclic aliphatic diol having a straight chain structure and having 2 to 3 carbon atoms. Examples of the acyclic aliphatic diol having a linear structure of 4 or less include ethylene glycol, 1, 3-propanediol, 1,4-butanediol, etc. are used. When the number of carbon atoms in the ol is small, ie, 4 or less, the polyester resin (A) is The weight ratio of carboxylic acids (a) with high biomass degree increases, and the biomass degree is increased. This is because it is possible.

[0049] [Production of polyester resin (A)] In the present invention, the polyester resin (A) is a mixture of a polyvalent carboxylic acid (a) and a polyol (b) in the presence of a catalyst by a known method. In the polycondensation reaction, the esterification reaction or the ester exchange reaction is carried out first. In addition, when it is not necessary to obtain a high molecular weight, an esterification reaction, Alternatively, it may be produced by only the transesterification reaction. When a polyol is used, the polyol is mixed with the polycarboxylic acid (a) and the polyol (b). Ethylene terephthalate may be added.

[0050] In such an esterification reaction or transesterification reaction, a catalyst is used. Examples of the titanium catalyst include tetraisopropyl titanate and tetrabutyl titanate. catalysts, antimony trioxide and other antimony-based catalysts, germanium dioxide and other germanium-based catalysts Examples of catalysts include catalysts such as zinc acetate, manganese acetate, and dibutyltin oxide. One or more of these can be used. Among these, those with high catalytic activity are Based on the balance between the color of the reaction product and the color of the product obtained, antimony trioxide, tetrabutyl titanate, , germanium dioxide, and zinc acetate are preferred.

[0051] The amount of the catalyst is 1 to 10,000 ppm based on the total copolymerization components (by weight). It is preferable that the concentration is 10 to 5000 ppm, particularly preferably 20 to 300 ppm. If the blending amount is too small, the polymerization reaction tends not to proceed sufficiently. On the other hand, if the amount is too large, there is no advantage such as shortening the reaction time, and side reactions tend to occur easily.

[0052] The reaction temperature during the esterification reaction or the ester exchange reaction is 200 to 300°C. is preferable, particularly preferably 210 to 280°C, and further preferably 220 to 260°C. If the reaction temperature is too low, the reaction will not proceed sufficiently, whereas if the reaction temperature is too high, decomposition or the like may occur. The reaction is usually carried out under normal pressure.

[0053] The polycondensation reaction carried out after the esterification reaction or transesterification reaction is carried out. The reaction conditions are the same as those used in the above esterification reaction or transesterification reaction. The catalyst is further blended in an approximately equal amount, and the reaction temperature is preferably 200 to 280° C., particularly preferably The reaction temperature was kept at 210-270°C, and the reaction system was gradually reduced in pressure until it reached 5 hPa or less. If the reaction temperature is too low, the reaction tends not to proceed sufficiently. If the temperature is too high, side reactions such as decomposition tend to occur.

[0054] Thus, a polyester resin (A) containing structural units derived from the compound (α1) is obtained. do.

[0055] The content of the structural unit derived from the compound (α1) in the polyester resin (A) is , 25 mol % or more, preferably 30 mol % or more, of the total polyester resin (A); More preferably, it is 35 mol % or more. The upper limit is usually 60 mol %, and preferably If the content is too low, the composition becomes too hard and the adhesive strength decreases. If the content is too high, the adhesive becomes too soft and the adhesive properties are somewhat reduced.

[0056] The number average molecular weight of the polyester resin (A) used in the polyester resin composition is 3 000 or more, preferably 3500 to 50000, more preferably 4000 to 400 00, particularly preferably 5000 to 30000, particularly preferably 6000 to 20000, The number average molecular weight is preferably 7,000 to 15,000. If the number average molecular weight is too large, handling becomes difficult. The polymer's properties are reduced, so a large amount of solvent is required, which increases the environmental load and reduces the number average molecular weight. If it is too thin, the adhesive properties when used as an adhesive will decrease.

[0057] The weight average molecular weight of the polyester resin (A) is preferably 10,000 or more. , more preferably 10,000 to 500,000, and even more preferably 20,000 to 30,000 0, particularly preferably 30,000 to 250,000, and particularly preferably 40,000 to 20,000 0, and most preferably 50,000 to 150,000. If the weight average molecular weight is too small, When used as an adhesive, the adhesive properties tend to decrease. If the weight average molecular weight is too large, As a result, handling becomes difficult, and a large amount of solvent is required, which tends to increase the environmental impact. There is.

[0058] The number average molecular weight and weight average molecular weight above are number average molecular weights converted into standard polystyrene molecular weights. The molecular weight and weight-average molecular weight were measured using a high-performance liquid chromatograph (Tosoh Corporation, HLC-832 0GPC) and column: TSKgel SuperMultipore HZ-M (exhaust Exclusion limit molecular weight: 2×10 6Theoretical plate number: 16,000 plates / unit; Packing material: styrene-divinyl The measurement was performed using two in-line tubes of 1,2-dimethylbenzene copolymer (filler particle size: 4 μm). It is something that can be done.

[0059] The biomass ratio of the polyester resin (A) is preferably 50% or more. More preferably, the content is 60% or more, even more preferably 70% or more, and particularly preferably 75%. That is all. The upper limit is 100%. If the biomass content is low, the environmental impact will be reduced. tends to be insufficient.

[0060] Here, the biomass degree of the polyester resin (A) is ) based on the total weight of the plant-derived raw materials used in producing the polyester resin (A). This is the weight ratio of the material incorporated into the resin, and is calculated as follows: . The biomass ratios of the polyvalent carboxylic acids (a) and polyols (b) are as follows: The biomass content is calculated by taking the weighted average of the biomass content of each of the plants. In addition, if the value obtained by any of the following calculation methods is within the above range, good.

[0061] (Calculation method) <When polycondensation reaction is involved> Biomass ratio (%) = (polyvalent carboxylic acids (a) in polyester resin (A) and (a) is the number of moles of carbon of the plant-derived monomer calculated from the molar ratio of (b) and (c) (number of moles of carbon of all constituent monomers in steric resin (A)) × 100

[0062] <When no polycondensation reaction is involved> Biomass ratio (%) = (the ratio of carbon of plant-derived monomers in polyester resin (A) (number of moles) / (number of moles of carbon of all constituent monomers in polyester resin (A)) × 100

[0063] The biomass ratio was determined by analyzing the composition ratio using NMR and calculating the carbon number of the plant-derived monomer. / It can also be determined by calculating the total number of carbon atoms.

[0064] Furthermore, the biomass ratio is based on the Tokyo Metropolitan Industrial Technology Research Center Research Report, No. 4, 20 The method used was described in the 2009 "Technology for identifying the origin of biofuels using natural radioactive carbon C-14." It can also be measured.

[0065] As a method for adjusting the biomass degree to a predetermined range, polyvalent carboxylic acids derived from plants or One option is to use plant-derived polyols as the main component, but the biomass content is not as high as that of conventional polyols. In view of the above, it is particularly preferable that the polyvalent carboxylic acids are derived from plants.

[0066] In the present invention, the recycled carbon content of the polyester resin (A) is 50% or more. From the viewpoint of reducing the environmental load, it is preferable that the ratio is 60% or more, more preferably 60% or more, and further preferably It is preferably 70% or more, and particularly preferably 75% or more, with the upper limit being 100%. Here, the recycled carbon usage rate of the polyester resin (A) is the polyester resin (A) (A) containing recycled carbon used in producing the polyester resin (A) The weight ratio of the raw material. Examples of the raw material containing the above-mentioned recycled carbon include plant-derived raw materials. and recycled polyethylene terephthalate (recycled PET).

[0067] The method for calculating the recycled carbon usage rate is the same as the method for calculating the biomass ratio above. That is, it is possible to: (Calculation method) <When polycondensation reaction is involved> Recycled carbon usage rate (%) = (polyvalent carboxylic acids (a) in polyester resin (A) and (a) / (moles of recycled carbon calculated from the molar ratio of (b) and polyol (b)) / (polyester resin (Number of moles of carbon of all constituent monomers in (A)) × 100

[0068] <When no polycondensation reaction is involved> Recycled carbon usage rate (%) = (number of moles of recycled carbon in polyester resin (A)) / (polyester resin (B)) (number of moles of carbon of all constituent monomers in polyester resin (A)) × 100

[0069] The glass transition temperature (Tg) of the polyester resin (A) is preferably −90 to 20 ° C., particularly preferably -60 to 0 ° C., and further preferably -50 If the glass transition temperature (Tg) is too high, the adhesiveness when used as an adhesive is low. If the temperature is too low, the heat resistance and cohesive strength tend to decrease. do.

[0070] The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) manufactured by TA Instruments. The measurement temperature range is -90 to 100°C. The ramp rate is 10° C. / min.

[0071] The ester group concentration of the polyester resin (A) is usually 2 mmol / g or more, and is preferably or 3 to 10 mmol / g, more preferably 3.6 to 6 mmol / g, and particularly preferably If the ester group concentration is too low, the polyester-based The resin (A) becomes soft, and if it is too soft, the adhesive properties tend to decrease.

[0072] The above ester group concentration (mmol / g) is the concentration of ester groups in 1 g of polyester resin (A). This refers to the number of moles of the cyclic bond, and can be calculated, for example, from the amount of the compound to be charged. The method is to use the lesser amount of polyvalent carboxylic acid (a) or polyol (b) in total. This is the value divided by body weight, and an example calculation formula is shown below. When the polyvalent carboxylic acids (a) and polyols (b) are charged in equal molar amounts, Either of the following calculation formulas may be used. In addition, monomers with both carboxyl and hydroxyl groups are used, and caprolactam is also used. When preparing polyester from methacrylate, etc., the calculation method will be changed appropriately.

[0073] <When the amount of polyvalent carboxylic acids (a) is small> Ester group concentration (mmol / g) = [(X1 / x1 × m1 + X2 / x2 × m2 + X3 / x3×m3···) / Z]×1000 X1, X2, X3: Amount of polyvalent carboxylic acid (a) (g) x1, x2, x3: molecular weight of polyvalent carboxylic acid (a) m1, m2, m3: number of carboxyl groups per molecule of polycarboxylic acid (a) Z: Finished weight (g) <When the amount of polyol (b) is small> Ester group concentration (mmol / g) = [(Y1 / y1×n1+Y2 / y2×n2+Y3 / y3×n3···) / Z]×1000 Y1, Y2, Y3: Amount of polyol (b) charged (g) y1, y2, y3: molecular weight of polyol (b) n1, n2, n3: the number of hydroxyl groups per molecule of polyol (b) Z: Finished weight (g)

[0074] The ester group concentration can also be measured by a known method such as NMR. For example, the ester group concentration of polyester resin (A) is 1 H-NMR measurement (proton nuclear magnetic resonance spectroscopy), 13 C-NMR measurement (carbon type nuclear magnetism) This can be done using a gas resonance spectroscopy.

[0075] The method for adjusting the ester group concentration is, for example, to adjust the number of carbon atoms of polyol (b) A method of selecting a polyol having a molecular weight of 4 or less, or a method of selecting a linear carboxylic acid as the polyvalent carboxylic acid (a) or a combination of both.

[0076] The heat of crystalline fusion of polyester resin (A) measured by a differential scanning calorimeter is usually 10 J / g or less, preferably 5 J / g or less, more preferably 2 J / g or less, and particularly preferably The key point is that no heat of fusion of crystals occurs. If the heat of fusion of crystals is too large, crystallinity will occur. The storage stability of the resin solution may decrease, and the stability and adhesive properties at low temperatures when made into an adhesive sheet may also decrease. tends to decline. The heat of crystal fusion is the energy consumed when heating and melting a crystallized substance. , can be measured by differential scanning calorimetry (DSC).

[0077] As a method for adjusting the heat of fusion of crystals, for example, a polyvalent carboxylate having an alkyl group on the side chain is used. A method of using polyols with alkyl groups on the side chains or carboxylic acids, or a method of using copolymer monomer components A method using three or more, preferably four or more, of the above components is exemplified.

[0078] The acid value of the polyester resin (A) is 10 mgKOH / g or less. It is preferable from the viewpoint of preventing dissolution and improving durability, and more preferably 5 mgKOH / g or less, particularly Preferably, it is 2 mgKOH / g or less, particularly preferably, it is 1 mgKOH / g or less, and most preferably If the acid value is too high, the durability tends to decrease. be. In order to adjust the acid value, for example, the polyimide may be added during the esterification reaction or the transesterification reaction. In addition, the acid value is reduced by increasing the ratio of aldehyde and adjusting the reaction conditions. The limit is usually 0 mg KOH / g.

[0079] The acid value of the polyester resin (A) is determined by neutralization titration according to JIS K0070. This is what is required. In the present invention, the acid value refers to the amount of carboxyl group contained in the polyester resin (A). The above carboxyl group means a carboxyl group neutralized with a basic compound. , and those in the carboxylate ion state are also included.

[0080] As described above, the polyester resin composition contains the polyester resin (A1) and In both cases, preferably, a polyisocyanate compound (B), a hydrolysis inhibitor (C), and if necessary, Depending on the requirements, tackifiers (D), urethane catalysts (E), antioxidants (F), etc. may be added. It is preferred. In addition to the polyester resin (A), the pressure-sensitive adhesive composition preferably contains a polyhydric Isocyanate compound (B), hydrolysis inhibitor (C), and optionally, tackifier (D ), a urethanization catalyst (E), an acid value inhibitor (F), etc. are preferably contained.

[0081] <Polyisocyanate compounds (B)> The polyester resin composition or the pressure-sensitive adhesive composition contains a polyisocyanate as a crosslinking agent. It is preferable that the composition further contains a polyisocyanate-based compound (B), and the polyisocyanate-based compound (B) By incorporating the polyisocyanate compound (B ) is crosslinked to give it excellent cohesive strength, improving the performance of the adhesive. do.

[0082] Examples of such polyisocyanate compounds (B) include 2,4-tolylene diisocyanate. Cyanate, tolylene diisocyanate crosslinking agents such as 2,6-tolylene diisocyanate , 1,3-xylylene diisocyanate and other xylylene diisocyanate-based crosslinking agents, Dif Diphenylmethane-based crosslinking agents such as phenylmethane-4,4-diisocyanate, 1,5-naphthalene Aromatic isocyanates such as naphthalene diisocyanate crosslinking agents such as toluene diisocyanate Diisocyanate crosslinking agent; isophorone diisocyanate, 1,4-cyclohexane diisocyanate 4,4'-Dicyclohexylmethane diisocyanate, Methylcyclohexane diisocyanate Cyanate, isopropylidenedicyclohexyl-4,4'-diisocyanate, 1,3 - Alicyclic isocyanates such as diisocyanatomethylcyclohexane and norbornane diisocyanate Isocyanate-based crosslinking agents; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate Aliphatic isocyanate crosslinking agents such as isocyanates; and the above isocyanate compounds Examples of the polyvalent isocyanurate include adducts, biuret, and isocyanurates. The isocyanate compound (B) is a compound in which the isocyanate portion is blocked with phenol, lactam, etc. These polyisocyanate compounds (B) can also be used. One type may be used alone, or two or more types may be used in combination.

[0083] When such a polyisocyanate compound (B) is used, its content is The molecular weight of the resin (A) can be appropriately selected according to the purpose of use. For one equivalent of at least one of the hydroxyl group and the carboxyl group contained in (A), The reactive groups contained in the socyanate compound (B) are multivalent in a ratio of 0.2 to 10 equivalents. It is preferable to contain an isocyanate compound (B), particularly preferably 0.5 to 5 equivalents. The amount of the polyisocyanate compound (B) is preferably 0.5 to 3 equivalents. If the equivalent number of the reactive group contained in is too small, the cohesive force tends to decrease, and if it is too large, There is a tendency for flexibility to decrease.

[0084] In addition, in the reaction between the polyester resin (A) and the polyisocyanate compound (B), The polyester resin (A) and the polyisocyanate compound (B) are Organic solvents that do not have reactive functional groups, for example, esters such as ethyl acetate and butyl acetate, Ketones such as methyl ethyl ketone and methyl isobutyl ketone, aromatics such as toluene and xylene Organic solvents such as aromatics can be used. These can be used alone or in combination of two or more. It is possible.

[0085] <Hydrolysis inhibitor (C)> The hydrolysis inhibitor (C) is a long-term It is contained as necessary to ensure long-term durability. As the hydrolysis inhibitor (C), a conventionally known one can be used. For example, Compounds that react with the carboxyl end of the polyester resin (A) to bond thereto are exemplified. Specifically, functional groups such as carbodiimide groups, epoxy groups, and oxazoline groups are Among these, compounds containing a carbodiimide group are particularly preferred. This is preferred because it is highly effective in eliminating the catalytic activity of the protons derived from the carboxyl group terminals.

[0086] The carbodiimide group-containing compound is usually a carbodiimide group (-N=C=N- ) in the molecule, but it is difficult to use them under high temperature and high humidity conditions. In order to improve the durability of the resin, a compound having two or more carbodiimide groups in the molecule, i.e., a polyimide compound, is used. It is preferable that the compound is a trivalent carbodiimide compound, and particularly preferable that the compound has three carbodiimide groups in the molecule. It is preferable that the compound contains at least one of these groups, more preferably at least five, and particularly preferably at least seven. The number of carbodiimide groups in a molecule is usually 50 or less, and If it is too large, the molecular structure becomes too large, which tends to reduce compatibility. It is produced by decarboxylation condensation reaction of diisocyanate in the presence of an imidization catalyst. It is also preferred to use a high molecular weight polycarbodiimide.

[0087] Furthermore, the terminal isocyanate groups of the high molecular weight polycarbodiimide are blocked with a blocking agent. In terms of storage stability, it is preferable to use a sealing agent that reacts with an isocyanate group. Examples of compounds that can be used include compounds that have active hydrogen or compounds that have an isocyanate group. For example, a carboxy group, an amino group, or an isocyanate group may be used. Monoalcohols, monocarboxylic acids, monoamines, and monoisocyanates. Examples include:

[0088] As such a high molecular weight polycarbodiimide, the following diisocyanates are used: Examples of such compounds include those obtained by polymerization reaction.

[0089] Such diisocyanates include, for example, 4,4'-diphenylmethane diisocyanate. , 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3' -Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl Diisocyanate, 3,3'-dimethyl-4,4'-diphenyl ether diisocyanate 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1- Methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4' -Dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate These can be used alone or in combination of two or more. The high molecular weight polycarbodiimide may be synthesized or a commercially available product may be used.

[0090] Commercially available carbodiimide group-containing compounds include, for example, Carbodiimide Among them, Carbodilite (registered trademark) series is (Registered trademark) "V-01", "V-02B", "V-03", "V-04K", "V-04P F", "V-05", "V-07", "V-09", and "V-09GB" are incompatible with organic solvents. This is preferred because of its excellent solubility.

[0091] Examples of the epoxy group-containing compound include glycidyl ester compounds and glycidyl Ether compounds and the like are preferred.

[0092] Examples of the glycidyl ester compound include benzoic acid glycidyl ester, t- Butylbenzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexa Glycidyl ester of carboxylic acid, glycidyl ester of pelargonic acid, glycidyl ester of stearate Glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, behenyl ester glycidyl ester of glycidyl oleate, glycidyl ester of versatic acid, glycidyl ester of glycidyl oleate Esters, glycidyl linoleate, glycidyl linoleate, behenol Acid glycidyl ester, stearolic acid glycidyl ester, diglycidyl terephthalate Ester, diglycidyl isophthalate, diglycidyl phthalate, naphtha Diglycidyl ester of diphenyl ether, diglycidyl ester of methyl terephthalic acid, Hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester , cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester , succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid Diglycidyl ester, Octadecanedicarboxylic acid diglycidyl ester, Trimellitic triglycidyl ester of pyromellitic acid, tetraglycidyl ester of pyromellitic acid, etc. These can be used alone or in combination of two or more.

[0093] Examples of the glycidyl ether compound include phenyl glycidyl ether, o- Phenyl glycidyl ether, 1,4-bis(β,γ-epoxypropoxy)butane, 1 ,6-bis(β,γ-epoxypropoxy)hexane, 1,4-bis(β,γ-epoxy 1-(β,γ-epoxypropoxy)benzene, 1-(β,γ-epoxypropoxy)-2-ethoxyethane, 1 -(β,γ-epoxypropoxy)-2-benzyloxyethane, 2,2-bis-[р- (β,γ-epoxypropoxy)phenyl]propane and 2,2-bis-(4-hydro Bisphenols such as 2,2-bis-(4-hydroxyphenyl)propane and 2,2-bis-(4-hydroxyphenyl)methane Examples include bisglycidyl polyether obtained by the reaction of phenol with epichlorohydrin. These can be used alone or in combination of two or more kinds.

[0094] The oxazoline group-containing compound is preferably a bisoxazoline compound. Specifically, for example, 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl- 2-oxazoline), 2,2'-bis(4,4-dimethyl-2-oxazoline), 2,2 '-Bis(4-ethyl-2-oxazoline), 2,2'-bis(4,4'-diethyl-2 -oxazoline), 2,2'-bis(4-propyl-2-oxazoline), 2,2'-bi Bis(4-butyl-2-oxazoline), 2,2'-bis(4-hexyl-2-oxazoline) 2,2'-bis(4-phenyl-2-oxazoline), 2,2'-bis(4-cyclohexyl) 2,2'-bis(4-benzyl-2-oxazoline), 2,2'-bis(4-benzyl-2-oxazoline) , 2,2'-p-phenylenebis(2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-o-phenylenebis(2-oxazoline), 2,2' -p-phenylenebis(4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4-dimethyl-2-oxazoline), 2,2'-m-phenylenebis(4-methyl 2,2'-m-phenylenebis(4,4-dimethyl-2-oxazoline), 2,2'-Ethylenebis(2-oxazoline), 2,2'-Tetramethylene Bis(2-oxazoline), 2,2'-hexamethylenebis(2-oxazoline), 2, 2'-Octamethylenebis(2-oxazoline), 2,2'-decamethylenebis(2-oxazoline) 2,2'-Ethylenebis(4-methyl-2-oxazoline), 2,2'- Tetramethylenebis(4,4-dimethyl-2-oxazoline), 2,2'-9,9'-di Phenoxyethane bis(2-oxazoline), 2,2'-cyclohexylene bis(2-oxazoline) Examples of such aryl ethers include 2,2'-diphenylenebis(2-oxazoline) and 2,2'-diphenylenebis(2-oxazoline). Among these, 2,2'-bis(2-oxazoline) is a polyester resin ( A) is the most preferable from the viewpoint of reactivity with A). These may be used alone or in combination of two or more. It is possible.

[0095] It is preferable that the hydrolysis inhibitor (C) has low volatility. It is preferable to use a polymer having a high molecular weight, usually 300 to 10,000, preferably 100 It ranges from 0 to 5000. In addition, as the hydrolysis inhibitor (C), a compound having a high weight average molecular weight is preferred from the viewpoint of hydrolysis resistance. It is preferable to use a hydrolysis inhibitor (C) having a weight average molecular weight of 500 or more. It is preferable that the number of the sieving rods is 1000 or more, more preferable that the number of the sieving rods is 2000 or more. It is more preferable that the weight average molecular weight is 3000 or more, and particularly preferable that the weight average molecular weight is 3000 or more. is usually 50,000. If the molecular weight of the hydrolysis inhibitor (C) is too small, the hydrolysis resistance tends to decrease. If the molecular weight is too large, the compatibility with the polyester resin (A) tends to decrease. do.

[0096] Among the hydrolysis inhibitors (C), it is preferable to use a carbodiimide group-containing compound. In this case, the carbodiimide equivalent is preferably 50 to 10,000, particularly 100 It is preferable that the carbodiimide equivalent is 1000 or less, and more preferably 150 to 500. indicates the formula weight per one carbodiimide group.

[0097] When the hydrolysis inhibitor (C) is used, its content is It is preferably 0.01 to 10 parts by weight, and particularly preferably The content is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight. If the amount is small, the mixture tends to become cloudy due to poor compatibility with the polyester resin (A). If the thickness is too large, it tends to be difficult to obtain sufficient durability.

[0098] The content of the hydrolysis inhibitor (C) is determined based on the acid value of the polyester resin (A). It is preferable to optimize the content accordingly, and the polyester resin ( The hydrolysis inhibitor (C) in the pressure-sensitive adhesive composition relative to the total mole number (x) of the acidic functional groups of A) The molar ratio ((y) / (x)) of the total number of moles of functional groups (y) is 0.5 or less (y) / (x). It is preferable that (y) / (x) is 1≦(y) / (x)≦1000, and it is particularly preferable that (y) / (x) is 1≦(y) / (x)≦1000, and it is further preferable that (y) / (x) is 1≦(y) / (x)≦1000. 1.5≦(y) / (x)≦100. If the molar ratio of (y) to (x) is too low, the moisture and heat resistance tends to decrease. If the molar ratio of (y) to (x) is too high, the compatibility with the polyester resin (A) becomes poor. The adhesive strength, cohesive strength and durability tend to decrease.

[0099] <Tackifier (D)> In the present polyester resin composition or the present pressure-sensitive adhesive composition, the adhesive properties are improved. It is preferable to contain a tackifier (D) in that a tackifier (D) can be added.

[0100] The tackifier (D) is not particularly limited, and any conventionally known tackifier may be used. Examples of the tackifier (D) include hydrocarbon tackifier resins, Terpene resin, phenolic resin, rosin resin, xylene resin, epoxy resin, Examples of the resins that can be used alone include triamide resins, ketone resins, and elastomer resins. Alternatively, two or more of them may be used in combination. Among them, hydrocarbon-based tackifier resins, terpene-based The tackifier (D) is preferably at least one hydrocarbon tackifier. It is particularly preferred that the tackifier contains a hydrocarbon-based tackifier resin, and the hydrocarbon-based tackifier resin accounts for 30% of the total tackifier. % by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more It is preferable that the above.

[0101] Examples of the hydrocarbon tackifier resin include aliphatic hydrocarbon resins and aromatic carbon resins. Hydrogen resin, aliphatic cyclic hydrocarbon resin, aliphatic and aromatic petroleum resin (styrene-olefin copolymers, aliphatic and alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone resins Examples of the resins include various hydrocarbon resins such as coumarone-indene resins. For example, the "FTR6100", "FTR6110", and "FTR61" manufactured by Mitsui Chemicals, Inc. 25", "FTR8100", "FTR8120", "FMR0150", etc. .

[0102] Examples of the terpene resin include terpene resin, terpene phenol resin, and and aromatic modified terpene resins. Specifically, α-pinene polymers, β-pinene Polymers, dipentene polymers, and their phenolic, aromatic, hydrogenated, and carbon-modified forms. A hydrochloric acid-modified terpene resin can be used. , "YS Polystar S145" and "YS Resin PX1000" manufactured by Yasuhara Chemical Co., Ltd. "YS Resin PX1250", "YS Polyster T160", "YS Polyster T145" ","YS Polyster T130,","YS Resin TO115,","YS Polyster G15 0", "YS Polyster G125", "YS Polyster U130", "Clearon P12 5" and others. Terpene-based adhesives are popular because of their good adhesion to non-polar substrates such as polypropylene. Resins are preferred, with terpene phenol resins being particularly preferred.

[0103] Examples of the phenol-based resin include phenol, m-cresol, 3,5-hydroxypropyl ether, and 1,2-diphenyl ether. Various phenols such as phenol, p-alkylphenol, and resorcinol, and formaldehyde Condensation products of the above phenols and formaldehyde can also be used. and a resol obtained by addition reaction of the phenols and formaldehyde in the presence of an alkali catalyst. Novolak, unmodified or modified rhodium, obtained by condensation reaction of aldehyde with acid catalyst. The rosin derivatives such as rosin and its derivatives are added with phenol under an acid catalyst and thermally polymerized. For example, a rosin-modified phenolic resin obtained by the method described above can be used.

[0104] Examples of the rosin-based resin include rosin resin, polymerized rosin resin, hydrogenated rosin resin, Rosin ester resin, hydrogenated rosin ester resin, rosin phenolic resin, polymerized rosin es Specifically, unmodified gum rosin, wood rosin, tall oil rosin, etc. Rosin (raw rosin) and its derivatives that have been hydrogenated, disproportionated, polymerized, or otherwise chemically modified. In addition, commercially available products such as rosin, "Hariestar TF", "Haritac 8LJA", and "Haritac PH" manufactured by Lima Chemical Co., Ltd. Examples include "Harritac FK100" and "Harritac PCJ".

[0105] The tackifier (D) preferably has an acid value of 30 mgKOH / g or less, and particularly preferably or 10 mgKOH / g or less, more preferably 6 mgKOH / g or less, and particularly preferably When multiple types of tackifiers (D) are used in combination, their average The average is preferably within the above range.

[0106] The softening point of the tackifier (D) (measured, for example, by the ring and ball method) is 80 to 170° C. It is preferable that the temperature is 90 to 165° C., particularly preferably 100 to 165° C. 160°C, more preferably 120 to 155°C, and particularly preferably 135 to 150°C. If the softening point is within the above range, the adhesive properties (adhesive strength, cohesive strength) can be improved. There is a tendency for this to be possible.

[0107] The tackifier (D) acts as a barrier for the polyester resin composition or the entire pressure-sensitive adhesive composition. In order to maintain a high degree of biomass, plant-derived tackifiers are preferred. Examples of the resin include terpene-based resins and rosin-based resins.

[0108] The tackifier (D) is preferably one having an aromatic structural unit from the viewpoints of improving cohesive strength and compatibility. As the tackifier containing an aromatic structural unit, an aromatic hydrocarbon is preferably used. Resins, aliphatic and aromatic petroleum resins (styrene-olefin copolymers, etc.), coumarone resins Examples include cellulose, coumarone-indene resin, terpene-phenol resin, and aromatic modified terpene resin. can be done.

[0109] When a tackifier (D) is used, its content is 100% by weight of the polyester resin (A). The amount is preferably 2 to 200 parts by weight, more preferably 5 to 150 parts by weight. parts by weight, more preferably 8 to 100 parts by weight, and particularly preferably 10 to 80 parts by weight. When the content is within the above range, the adhesive properties (adhesion This tends to improve the strength of the bond (strength, cohesion).

[0110] <Urethanization catalyst (E)> The present polyester resin composition or the present pressure-sensitive adhesive composition is preferably a urethane catalyst in terms of reaction rate. It is more preferable that the catalyst (E) is contained.

[0111] Examples of the urethane-forming catalyst (E) include organometallic compounds and tertiary amine compounds. These can be used alone or in combination of two or more.

[0112] Examples of the organometallic compounds include zirconium compounds, iron compounds, tin compounds, and the like. Examples of compounds include titanium compounds, lead compounds, cobalt compounds, and zinc compounds. can.

[0113] Examples of the zirconium-based compound include zirconium naphthenate, zirconium Acetylacetonate and the like. Examples of the iron-based compound include iron acetylacetonate and iron 2-ethylhexanoate. etc. Examples of the tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dichloride ... butyltin dilaurate and the like. Examples of the titanium-based compound include dibutyltitanium dichloride and tetrabutyltitanium dichloride. rutitanium trichloride, butoxytitanium trichloride, etc. Examples of the lead-based compounds include lead oleate, lead 2-ethylhexanoate, and lead benzoate. Examples of suitable lead include lead and lead naphthenate. Examples of the cobalt-based compound include cobalt 2-ethylhexanoate and cobalt benzoate. Barto et al. Examples of the zinc-based compounds include zinc naphthenate and zinc 2-ethylhexanoate. Some examples include:

[0114] Examples of the tertiary amine compound include triethylamine and triethylenediamine. amine, 1,8-diazabicyclo-(5,4,0)-undecene-7, and the like.

[0115] Among these urethane catalysts (E), the following are the most suitable in terms of reaction rate and pot life of the adhesive layer: Organometallic compounds are preferred, and zirconium compounds are particularly preferred. It is preferable to use acetylacetone in combination with the catalyst (E) as a catalytic inhibitor. The inclusion of diacetone suppresses catalytic activity at low temperatures and extends the pot life. preferable.

[0116] When the urethane catalyst (E) is used, the content thereof is 1 / 1 The amount is preferably 0.0001 to 1 part by weight, particularly preferably 0.001 to 1 part by weight, based on 0.000 parts by weight. The content is preferably 0.1 parts by weight, more preferably 0.01 to 0.05 parts by weight. If the amount is too small, the aging time until the crosslinking reaction is completed tends to be long, and if the amount is too large, the viscosity The wearability tends to decrease.

[0117] <Antioxidants (F)> The polyester resin composition or the pressure-sensitive adhesive composition is preferably made of an acid in order to increase the stability of the resin. It is more preferable that the composition contains an antioxidant (F).

[0118] Examples of the antioxidant (F) include hindered phenol-based antioxidants, amines, etc. Among them, hindered oxidation inhibitors are particularly useful. The antioxidant is selected from the group consisting of phenol-based antioxidants, amine-based antioxidants, and phosphoric acid-based antioxidants. It is preferable that the compound is at least one of the above-mentioned compounds, and particularly preferable that the compound is a hindered phenol compound. Antioxidants that are Examples of hindered phenol-based antioxidants include those having a phenolic hydroxyl group bonded thereto. At least one of the carbon atoms adjacent to the carbon atom on the aromatic ring has a tertiary butyl group or the like. Antioxidants that have a hindered phenol structure with a highly hindered group attached include .

[0119] When the antioxidant (F) is used, its content is 100% by weight of the polyester resin (A). The ratio is preferably 0.01 to 10 parts by weight, and more preferably 0.03 to 8 parts by weight. parts by weight, and more preferably 0.05 to 5 parts by weight. If the content is too low, adhesive residue on the adherend tends to be easily generated, and if the content is too high, If the adhesive is used, the adhesive properties tend to decrease.

[0120] In the present polyester resin composition or the present pressure-sensitive adhesive composition, Resin (A), polyisocyanate compound (B), hydrolysis inhibitor (C), tackifier In addition to (D), the urethane catalyst (E) and the antioxidant (F), any other additives that do not impair the effects of the present invention may be used. In the range, additives such as softeners, UV absorbers, stabilizers, antistatic agents, etc., and other inorganic Alternatively, powders such as organic fillers, metal powders, pigments, and other particulate additives can be added. In addition, the polyester resin composition or the adhesive composition may contain the above-mentioned components as raw materials for production. The material may contain small amounts of impurities. These can be used alone or in combination of two or more.

[0121] The polyester resin composition or the pressure-sensitive adhesive composition can be prepared, for example, by A steric resin (A) and optional components as required are prepared, and a polyester resin (A ) during the manufacturing process, or by dissolving polyester in an organic solvent. The resulting mixture is mixed with a solution of the resin (A) and dispersed using a mixing roller. This can be done.

[0122] The polyester resin composition or the pressure-sensitive adhesive composition has a biomass ratio of 50% or more. It is preferable from the viewpoint of reducing the environmental load, more preferably 60% or more, and further preferably 7 0% or more, particularly preferably 80% or more, particularly preferably 85% or more, and most preferably 90 The biomass degree of the polyester resin composition or the pressure-sensitive adhesive composition is 5% or more. , by adjusting the type and amount of polyester resin (A) and other compounding ingredients. It is possible. The biomass degree of the polyester resin composition or the pressure-sensitive adhesive composition is The polyester resin composition relative to the total weight of the polyester resin composition or the pressure sensitive adhesive composition The weight ratio of the plant-derived raw materials used in the production of the adhesive composition is, for example, For example, it can be calculated using the following formula. Biomass ratio (%)=[(Present polyester resin composition or present pressure-sensitive adhesive composition (Biomass content of each plant-derived raw material used in the production of the polyester resin composition or is the weight of each plant-derived raw material used in producing the present adhesive composition) / (the present adhesive composition (total weight of the ester resin composition or the present pressure sensitive adhesive composition) × 100

[0123] The biomass degree of the polyester resin composition or the pressure-sensitive adhesive composition is as described above. It can also be measured by NMR or natural radioactive carbon C-14. In addition, if the value obtained by any of the above calculation methods falls within the above range, That's fine.

[0124] The polyester resin composition or the adhesive composition contains 50% or more recycled carbon. It is preferable from the viewpoint of reducing the environmental load, more preferably 60% or more, and further preferably It is preferably 70% or more, and more preferably 75% or more, with the upper limit being 100%. Here, the recycled carbon usage rate of the polyester resin composition or the pressure-sensitive adhesive composition is , the polyester resin composition or the pressure-sensitive adhesive composition, of the weight of the raw material containing recycled carbon used in producing the resin composition or the present pressure-sensitive adhesive composition. The ratio is 100%. Examples of raw materials containing recycled carbon include plant-derived raw materials and recycled polyethylene terephthalate. The polyester resin composition may be, for example, a terephthalate (recycled PET). The recycled carbon content of the adhesive composition is determined by the ratio of the polyester resin (A) and other blended components. The amount can be adjusted by changing the type and amount of the ingredient. The recycled carbon usage rate of the polyester resin composition or the pressure-sensitive adhesive composition is, for example, , can be calculated by the following formula. Recycled carbon usage rate (%) = (the polyester resin composition or the pressure-sensitive adhesive composition produced) (Recycled carbon usage rate of each plant-derived raw material used in producing the polyester resin composition) × ( or the total weight of each raw material using recycled carbon used in producing the present adhesive composition) / (Total weight of the polyester resin composition or the pressure sensitive adhesive composition)×100

[0125] The polyester resin composition can be suitably used as a pressure-sensitive adhesive composition. Hereinafter, the pressure-sensitive adhesive composition comprising the polyester resin composition and the pressure-sensitive adhesive composition will be collectively referred to as "composition for adhesive" and "composition for adhesive" below. It will be referred to simply as the "adhesive composition." In addition, the adhesive according to one embodiment of the present invention (hereinafter referred to as "the adhesive") is The adhesive composition is crosslinked.

[0126] The pressure-sensitive adhesive sheet according to one embodiment of the present invention (hereinafter referred to as "the pressure-sensitive adhesive sheet") is The adhesive layer is formed on one side of a support substrate. It is preferred that the protective layer is formed on one or both surfaces. In the present invention, the term "sheet" includes "film" and "tape." This is what is stated.

[0127] <Adhesive sheet> The pressure-sensitive adhesive sheet can be produced, for example, as follows. The present pressure-sensitive adhesive sheet can be manufactured according to a known method for manufacturing a pressure-sensitive adhesive sheet. For example, the pressure-sensitive adhesive composition can be applied to a substrate, dried, and then a pressure-sensitive adhesive layer can be formed on the opposite side. A release sheet is attached to the adhesive layer surface, and if necessary, cured to form a film containing the adhesive on the substrate. Thus, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer is obtained.

[0128] The pressure-sensitive adhesive composition is applied to a release sheet, dried, and a substrate is attached to the opposite side of the pressure-sensitive adhesive layer. and optionally curing the resulting adhesive sheet.

[0129] In addition, a pressure-sensitive adhesive layer is formed on a release sheet, and a release sheet is attached to the opposite side of the pressure-sensitive adhesive layer. This makes it possible to produce a substrate-less double-sided PSA sheet.

[0130] When using the obtained pressure-sensitive adhesive sheet or substrate-less double-sided pressure-sensitive adhesive sheet, the release sheet is adhered to the sheet. The adhesive layer is peeled off and the adhesive layer is attached to the adherend.

[0131] Examples of the substrate include polyethylene naphthate, polyethylene terephthalate, Polybutyrene terephthalate, polyethylene terephthalate / isophthalate copolymer, etc. Polyester resins such as polyethylene, polypropylene, polymethylpentene, etc. olefin resins; polyvinyl fluoride, polyvinylidene fluoride, polyethylene fluoride, etc. Fluorinated ethylene resin; nylon 6, nylon 6,6 and other polyamides; polyvinyl chloride, Polyvinyl chloride / vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl vinyl alcohol copolymers, polyvinyl alcohol, vinylon and other vinyl polymers; triacetic acid cellulosic acid Cellulosic resins such as cellulose and cellophane; polymethyl methacrylate, polymethacrylic acid acrylic resins such as polystyrene, polyethyl acrylate, polybutyl acrylate, etc. Polyimide; cycloolefin polymer; polycarbonate; polyarylate; A sheet made of at least one synthetic resin selected from the group consisting of aluminum, copper, and iron. Metal foil; paper such as wood-free paper and glassine paper; textiles made of glass fiber, natural fibers, synthetic fibers, etc. Nonwoven fabrics are examples of such substrates. These substrates may be used as single-layer structures or as multi-layer structures in which two or more types of substrates are laminated. It can be used as:

[0132] Among these, the substrates made of polyethylene terephthalate and polyimide are particularly preferred. Of these, polyethylene terephthalate is particularly preferred because of its excellent adhesiveness to pressure-sensitive adhesives.

[0133] The substrate may also be a foam substrate, for example, polyurethane foam or polyethylene foam. A foam sheet made of a synthetic resin foam such as polyacrylate foam is used. Among these, it is particularly noteworthy for its excellent balance of conformability to the adherend and adhesive strength. Of these, polyethylene foam and polyacrylate foam are preferred.

[0134] The thickness of the substrate is preferably, for example, 1 to 1000 μm, and particularly preferably The thickness is preferably 2 to 500 μm, and more preferably 3 to 300 μm.

[0135] Examples of the release sheet include sheets made of various synthetic resins exemplified above as the base material. Paper, cloth, nonwoven fabric, etc. that have been treated with a release agent can be used. It is preferable to use a release sheet of a polymeric type.

[0136] The pressure-sensitive adhesive composition can be applied by, for example, a gravure roll coater or a reverse roll coater. Roll coater, kiss roll coater, dip roll coater, bar coater, knife coater A coater, a spray coater, a comma coater, or the like may be used.

[0137] The conditions for the above curing treatment are usually room temperature (23°C) to 70°C, and the time is usually 1 to 24 hours. Specifically, for example, at 23° C. for 1 to 20 days, preferably at 23° C. for 3 to 1 The incubation may be performed under conditions such as 4 days at 40° C. for 1 to 10 days.

[0138] As for the drying conditions, the drying temperature is preferably 60 to 140° C., and more preferably 80 to The drying temperature is 120° C., and the drying time is preferably 0.5 to 30 minutes, and particularly preferably 1 to 5 minutes. be.

[0139] The thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet or substrate-less double-sided pressure-sensitive adhesive sheet is 2 to 500 μm. It is preferable that the thickness is 5 to 200 μm, particularly preferably 10 to 100 μm. If the thickness of the adhesive layer is too thin, the adhesive strength tends to decrease, whereas if it is too thick, the adhesive layer may not be uniformly adhered. In addition, it becomes difficult to apply the coating, and there is a tendency for defects such as air bubbles to occur in the coating. When shock absorption is taken into consideration, the thickness is preferably 50 μm or more.

[0140] The thickness of the adhesive layer was measured using a Mitutoyo ID-C112B adhesive sheet. The thickness of the entire sheet is measured by subtracting the thickness of the components other than the adhesive layer. It is required.

[0141] The gel fraction of the adhesive layer of the above-mentioned adhesive sheet is set to 10% by weight from the viewpoints of durability and adhesive strength. % or more, particularly preferably 20 to 80% by weight, and further preferably 30 If the gel fraction is too low, the cohesive strength decreases, and the retention strength decreases. If the gel fraction is too high, the adhesive strength tends to decrease due to an increase in cohesive strength. be.

[0142] The gel fraction is an index of the degree of crosslinking and is calculated, for example, by the following method. That is, a pressure-sensitive adhesive layer is formed on a polymer sheet (e.g., PET film, etc.) that serves as a substrate. The adhesive sheet (without a release sheet) is wrapped in a 200 mesh SUS wire net. The adhesive was then immersed in toluene at 23°C for 24 hours, and the weight of the adhesive component after immersion was calculated based on the weight of the adhesive component before immersion. The weight percentage of the undissolved adhesive component remaining in the wire mesh is the gel fraction. Subtract the weight.

[0143] The adhesive strength of this adhesive sheet under the following conditions is preferably 7N / 25mm or more. More preferably, it is 10N / 25mm or more, and particularly preferably, it is 12N / 25mm or more. The upper limit of the adhesive strength is usually 100N / 25mm, preferably 50N / 25mm. It is. [conditions] The adhesive sheet was attached to a polypropylene plate and left at 23°C and 50% RH for 30 minutes. After leaving it for 10 minutes, the 180 degree peel strength (N / 25mm).

[0144] Furthermore, the present pressure-sensitive adhesive sheet may be provided with a release sheet on the outer side of the pressure-sensitive adhesive layer as required. In the case of a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is formed on one side of a substrate, By applying a release treatment to the surface of the material opposite to the adhesive layer, the adhesive can be applied by using the release-treated surface. It is also possible to protect the agent layer.

[0145] The pressure sensitive adhesive can be used for bonding various members, and is particularly useful for bonding optical members. Single-sided or double-sided adhesive sheets for bonding, fixing components in portable electronic devices, fixing electronic components It is used for single-sided or double-sided adhesive sheets for fixed purposes. EXAMPLES

[0146] The present invention will be described in more detail below with reference to examples, but the present invention will not go beyond the gist of the invention. The present invention is not limited to the following examples. In the examples, "parts" and "%" indicate Weight basis is meant.

[0147] In the following examples, the number average molecular weight, weight average molecular weight, and Biomass degree, recycled carbon usage rate, glass transition temperature, gel fraction of adhesive layer, polyester resin Regarding the measurement of the biomass content and the recycled carbon usage rate of the adhesive composition (adhesive composition), The measurements were performed according to the method.

[0148] The polyester resins were produced by the following method (see Table 1).

[0149] [Examples 1-2, Comparative Examples 1-2] [Production of polyester resins (A) [A-1, A-2] and (A') [A'-1 to A'-2]] Construction] A reactor equipped with a thermometer, stirrer, distillation column, nitrogen inlet tube, and vacuum device was charged as shown in Table 1. The polyvalent carboxylic acids and polyols are mixed, and tetrabutyl titanate is used as a catalyst. The mixture was charged at 0.2 mmol / mol relative to polycarboxylic acids, and the internal temperature was gradually increased to 240°C. The temperature was then increased to 260°C and the esterification reaction was carried out for 4 hours. Tetrabutyl titanate is used at a ratio of 0.2 mmol / mol to polyvalent carboxylic acids. The pressure is then reduced to 1.33-2.66 hPa, and the polymerization reaction is carried out over 2-3 hours. A steric resin (A) was produced. The composition ratio and various physical properties of the resulting polyester resin (A) are shown in Table 2 below. In the above production, the plant-derived raw material is hydrodistilled dimer acid (hydrodistilled dimer acid having 44 carbon atoms). Hydrogenated C44 dimer acid), Hydrogenated C36 dimer acid (hydrogenated C36 dimer acid) In addition, some of the terephthalic acid and ethylene glycol were It is derived from polyethylene terephthalate (PET).

[0150] [Table 1]

[0151] [Table 2]

[0152] Next, prior to preparing the polyester resin composition (adhesive composition), the following steps are carried out: Each component was prepared as follows.

[0153] [Polyisocyanate compound (B)] Polyisocyanate compounds (B-1): "Coronate L55E, solids concentration 55%" (Manufactured by Tosoh Corporation)

[0154] [Hydrolysis inhibitor (C)] Carbodiimide compound (C-1): Carbodilite V-09GB, solid content 70 %" (Nisshinbo Chemical Co., Ltd.)

[0155] [Tackifier (D)] Terpene phenol resin (D-1): "YS Polyster T160, softening point 160℃" (Manufactured by Yasuhara Chemical Co., Ltd.) Terpene phenol resin (D-2): "YS Polyster G150, softening point 150℃" (Manufactured by Yasuhara Chemical Co., Ltd.) Terpene phenol resin (D-3): "YS Polyster S145, softening point 145℃" (Manufactured by Yasuhara Chemical Co., Ltd.)

[0156] The above polyester resin (A) or (A') and polyisocyanate compound (B) Using the hydrolysis inhibitor (C) and tackifier (D), the following composition shown in Table 3 was prepared. As described above, a polyester resin composition (adhesive composition) was prepared, and an adhesive sheet was produced.

[0157] [Examples 1-1 to 2-4, Comparative Examples 1-1 to 2-4] The polyester resin (A or A') obtained above was concentrated in ethyl acetate to give a solid content. Dilute to 50% and mix in the ratio (solid content) shown in Table 3 to make a polyisocyanate-based solution. The mixture (B-1) and the carbodiimide compound (C-1) are mixed and stirred to obtain a polyester resin. A terephthalate resin composition (adhesive composition) was obtained. The obtained adhesive composition was applied to polyethylene terephthalate (PET) sheets so that the thickness after drying was about 25 μm. After applying it to a polyethylene terephthalate (PET) film (thickness 38 μm), it was dried at 100°C for 3 minutes. A release-treated PET film (release The surface was protected with a film (type film), and the material was left to cure for 10 days in an atmosphere at 40°C. I got a seat.

[0158] The obtained pressure-sensitive adhesive sheets of the Examples and Comparative Examples were evaluated as follows. This is shown in Table 3 below.

[0159] <Initial adhesive strength (peel strength) (to SUS-BA)> A SUS-BA plate was prepared as the adherend. The pressure-sensitive adhesive sheet obtained above was heated at 23°C and 50% After cutting to 25mm x 200mm in a RH environment, peel off the release film and expose the adhesive layer side. The plate was pressed against a SUS-BA plate and a 2 kg roller was moved back and forth to press and bond the plate. After leaving it for 30 minutes under atmospheric pressure, the plate was placed on an autograph (Shimadzu Corporation, Autograph AGS- H 500N) at a peel speed of 300 mm / min and a 180 degree peel strength (N / 25m m) was measured and the state of peeling was visually observed.

[0160] <Adhesive strength after 72 hours (peel strength) (to SUS-BA)> A SUS-BA plate was prepared as the adherend. The pressure-sensitive adhesive sheet obtained above was heated at 23°C and 50% After cutting to 25mm x 200mm in a RH environment, peel off the release film and expose the adhesive layer side. The plate was pressed against a SUS-BA plate and a 2 kg roller was moved back and forth to press and bond the plate. After leaving it for 72 hours under atmospheric pressure, the plate was then measured using an autograph (Shimadzu Corporation, Autograph AGS- H 500N) at a peel speed of 300 mm / min and a 180 degree peel strength (N / 25m m) was measured and the state of peeling was visually observed.

[0161] <Initial adhesive strength (peel strength) (against PP)> A polypropylene (PP) plate was prepared as the adherend. After cutting to 25mm x 200mm in an environment of ℃ and 50% RH, the release film was peeled off. The adhesive layer side was placed against a PP plate, and a 2 kg roller was used to press and adhere the film. After leaving it for 30 minutes under atmospheric conditions, the plate was placed on an autograph (Shimadzu Corporation, Autograph AGS -H 500N) at a peel speed of 300 mm / min and a 180 degree peel strength (N / 25 The peeling state was visually observed.

[0162] <Holding force (cohesive force)> The pressure-sensitive adhesive sheet obtained above was subjected to a JIS Z-0237 test using SUS304 as the adherend. After applying the tape to an area of ​​25mm x 25mm, it was left to stand at 80℃ for 20 minutes. A load of 1 kg was applied and the displacement was measured after 24 hours.

[0163] [Table 3]

[0164] From the results in Table 3 above, the pressure-sensitive adhesive sheets of Examples 1-1 to 2-4 had excellent initial adhesion to metal adherends. It has excellent adhesion to difficult-to-adhere substrates such as polyolefin resins. The adhesive had the desired adhesiveness to the adhesive layer and had an excellent balance between adhesive strength and holding strength. In addition, in the pressure-sensitive adhesive sheets of Comparative Examples 1-1 to 2-4, the initial adhesion and adhesion after aging to the metal adherend were Although it has excellent adhesive properties, it has poor adhesion to polyolefin substrates. The effects were not entirely satisfactory. [Industrial Applicability]

[0165] The polyester resin composition or the pressure-sensitive adhesive composition is a polyester with a high biomass content. Even if a polyester resin is used, when it is used as an adhesive, it can be used on various adherends such as metals and plastics. It has excellent adhesive properties to the surface of the optical components. or double-sided adhesive sheets, single-sided or double-sided adhesives for fixing components of portable electronic devices, and electronic components It is used for contact sheets, etc.

Claims

1. A polyester-based resin composition containing a polyester-based resin, The polyester resin is a structural unit derived from a polyvalent carboxylic acid (a) and a polyol (b). unit, and derived from at least one of the polyvalent carboxylic acids (a) and the polyol (b). As the structural unit of the compound, a small amount of dimer acids having 44 carbon atoms and dimer diols having 44 carbon atoms are used. At least one structural unit derived from the compound (α1), and the content ratio of the structural unit derived from at least one compound (α1) in the dimer diol is 25 mol % or more of the total of structural units derived from polyvalent carboxylic acids (a) and polyol (b). and the number average molecular weight of the polyester resin (A1) is 3,000 or more. The polyester resin composition is characterized by the above-mentioned.

2. The polyester resin (A1) has a weight average molecular weight of 10,000 or more.

2. The polyester resin composition according to claim 1,

3. The polyester resin composition is characterized in that the biomass ratio is 50% or more.

3. The polyester resin composition according to claim 1 or 2.

4. The composition according to any one of claims 1 to 3, further comprising a polyisocyanate compound (B). The polyester resin composition according to any one of claims 1 to 5.

5. 5. The composition according to claim 1, further comprising a hydrolysis inhibitor (C). Item 1. The polyester resin composition according to item 1.

6. A pressure-sensitive adhesive composition containing a polyester resin, The polyester resin is a structural unit derived from a polyvalent carboxylic acid (a) and a polyol (b). unit, and derived from at least one of the polyvalent carboxylic acids (a) and the polyol (b). As the structural unit of the compound, a small amount of dimer acids having 44 carbon atoms and dimer diols having 44 carbon atoms are used. A polyester resin (A) containing a structural unit derived from at least one compound (α1).

1. A pressure-sensitive adhesive composition comprising:

7. The adhesive according to claim 6, characterized in that the adhesive strength under the following conditions is 7 N / 25 mm or more. Agent composition. Adhesive strength: When an adhesive layer made of the adhesive composition is formed on a substrate to form an adhesive sheet, the adhesive strength is After attaching it to a polypropylene plate and leaving it for 30 minutes in a 23°C, 50% RH environment, , 180 degree peel strength (N / 25 mm) from an adherend at a peel speed of 300 mm / min.

8. A pressure-sensitive adhesive, characterized in that the pressure-sensitive adhesive composition according to claim 6 or 7 is crosslinked.

9. A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive according to claim 8.

10. A double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive according to claim 8. 。

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