TW201908450A - Adhesive composition - Google Patents

Abstract

Provided is an adhesive agent composition that has excellent adhesiveness, application performance and solvent resistance, and that firmly adheres a urethane porous layer to a substrate film. The adhesive agent composition contains: an amorphous polyester resin (A) having a number-average molecular weight of 5,000 to 40,000, a glass transition temperature of 20 DEG C or less, and an acid value of 5 to 400 equivalents/106 g; an amorphous polyurethane resin (B) having a number-average molecular weight of 5,000 to 60,000 and a glass transition temperature of 50 DEG C or higher; and a polyisocyanate (C).

Description

Adhesive composition

The present invention relates to an adhesive composition having excellent adhesion, coating properties, and solvent resistance. Specifically, it relates to a wet film laminate sheet and a polishing pad formed using the wet film laminate sheet, and more specifically, it relates to a laminate obtained by laminating a porous urethane layer on a polyester film. Wet film laminates, and suitable for the surface of electronic parts such as liquid crystal glass, glass discs, photomasks, silicon wafers, CCD cover glass, etc. obtained by removing the skin layer Precision-ground abrasive pads.

A wet film laminate obtained by laminating a wet-solidified urethane honeycomb porous film (hereinafter referred to as a wet film) on a polyester film has been used in electronics for a long time. Polishing pads for precision polishing of parts.

Conventionally, as described above for the wet film laminate, a polyester film is coated with a solution of a polyurethane prepolymer to form a wet film, and then the film is peeled from the polyester film, and the adhesive The adhesive is obtained by attaching to another polyester film. When forming a polishing pad, the surface layer of the wet film is removed by grinding, polishing, or the like in advance to make a suede-like film on the surface, and then it is attached to another polyester film. When the wet film is temporarily peeled from the polyester film as described above, and is attached to another polyester film by using an adhesive, the conventional polyester film and the wet film lack adhesion with each other and cannot be used in Used directly as an abrasive pad without using an adhesive. However, in the above method, when the wet film is peeled from the polyester film, there is a problem that the wet film is easily deformed, and cracks and cuts may occur. Therefore, the type of polyurethane used is limited, and the thickness of the wet film is also limited. In addition, the polishing pad used for precision polishing requires the accuracy of flatness (concave and convexity on the surface), which complements the development of measuring equipment for precision polishing surfaces in recent years. The quality from users has become higher and more precise polishing pads are required. However, if the wet film is attached to the polyester film by using an adhesive as described above, there are also problems such as the flatness accuracy of the wet film surface being affected by the unevenness of the adhesive, resulting in poor flatness accuracy. problem.

It has also been proposed to obtain a wet film laminate sheet that can achieve high accuracy when used as a polishing pad without the step of temporarily peeling and attaching the wet film from the polyester film to another polyester film (for example, patent document 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3723897

[Problems to be Solved by the Invention]

However, the aforementioned methods have problems such as limitation of the base film, and need to be extended and heat-fixed after applying the easily-adhesive aqueous coating solution.

The present invention is an adhesive composition excellent in adhesiveness, coating property, and solvent resistance of a urethane porous layer and a base film that are well adhered. The adhesive composition of the present invention does not pick a substrate film, and can obtain a wet film laminated sheet without passing through the steps of temporarily peeling and attaching the wet film from the polyester film to another polyester film as described above. And polishing pads. [Means for solving problems]

As a result of diligent research by the inventors of the present case, it was found that the above-mentioned problems can be solved by the means shown below, and the present invention has been reached. That is, the present invention has the following constitution.

An adhesive composition comprising: an amorphous polyester resin (A) having a number average molecular weight of 5,000 to 40,000, a glass transition temperature of 20 ° C or lower, and an acid value of 5 to 400 equivalents / 10 ⁶ g; An amorphous polyurethane resin (B) having a glass transition temperature of 50 ° C. or higher and a polyisocyanate (C) of 5000 to 60,000.

The amorphous polyester resin (A) is preferably one having two or more carboxyl groups at the end of the resin. The blend ratio of the amorphous polyester resin (A) and the amorphous polyurethane resin (B) is The amorphous polyurethane resin (B) is preferably 5 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the amorphous polyester resin (A).

A laminated body is obtained by laminating an adhesive layer composed of the aforementioned adhesive composition and a plastic film. A laminated body is obtained by laminating a resin on the surface of the adhesive layer. A polishing pad is provided with a polishing layer on a part of the laminated body. [Effect of the invention]

The adhesive composition of the present invention has excellent adhesion to the urethane porous layer and the substrate film, and also has excellent coating properties and solvent resistance. Further, the adhesive composition of the present invention does not pick a substrate film, and can obtain a wet film laminate sheet and the step of temporarily peeling and attaching the wet film from the polyester film to another polyester film, and Polishing pad.

<Amorphous polyester resin (A)> The amorphous polyester resin (A) used in the present invention is preferably a polyester having a polycarboxylic acid component and a polyol component as copolymerization components, and a dicarboxylic acid component and A diol component is more preferable as a copolymerization component.

The dicarboxylic acid component constituting the amorphous polyester resin (A) is not particularly limited, and examples thereof include an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and an alicyclic dicarboxylic acid. The aromatic dicarboxylic acid is particularly preferably used. With aliphatic dicarboxylic acids.

As for the copolymerization amount of the aromatic dicarboxylic acid, when the total amount of the carboxylic acid component is 100 mol%, it is preferably 50 mol% or more, and more preferably 60 mol% or more. If it is too small, the humidity and heat resistance may decrease. Moreover, it is preferably 90 mol% or less, and more preferably 80 mol% or less. If it is too much, the adhesion to the substrate may be reduced.

Specific examples of the aromatic dicarboxylic acid are not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 4,4 '-Diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, etc., These can be used alone or in combination of two or more kinds. Among them, from the viewpoint of moist heat resistance, terephthalic acid and isophthalic acid are particularly preferably used.

The aliphatic dicarboxylic acid is not particularly limited, and an aliphatic dicarboxylic acid having 4 to 18 carbon atoms is preferably used. The more preferable carbon number of the aliphatic dicarboxylic acid is 5 or more, and the more preferable is 6 or more carbon number. The carbon number is preferably 10 or less. As for the copolymerization amount of the aliphatic dicarboxylic acid, when the total amount of the carboxylic acid component is 100 mol%, it is preferably 50 mol% or less, and more preferably 40 mol% or less. If it is too much, the humidity and heat resistance may decrease. In addition, it is preferably 10 mol% or more, and more preferably 20 mol% or more. If it is too small, the adhesion to the substrate may be reduced.

Specific examples of the aliphatic dicarboxylic acid are not particularly limited, and examples thereof include adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and octadecanoic acid. These can be used alone or in combination of two types. Used above. Among them, considering the viewpoint of acquisition, adipic acid and sebacic acid are particularly suitable.

As for the copolymerization amount of the alicyclic dicarboxylic acid, when the total amount of the carboxylic acid component is 100 mol%, it is preferably 50 mol% or less, more preferably 40 mol% or less, and most preferably 30 mol. % Or less, particularly preferably 20 mol% or less, most preferably 10 mol% or less, and 0 mol% is not a problem. If it is too large, a polyester resin excellent in moisture resistance may not be obtained in some cases. Specific examples of the alicyclic dicarboxylic acid are not particularly limited, and examples thereof include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer acid, etc. These can be used alone or in combination of two or more kinds. Among these, from the viewpoint of availability, 1,4-cyclohexanedicarboxylic acid is particularly preferably used.

In order to impart acid value and branching to the amorphous polyester resin (A), a polycarboxylic acid anhydride is preferably used. More preferred is a polyvalent carboxylic acid anhydride of 3 or more members. By providing an acid value and a branch, improvement in reactivity with polyisocyanate (C) can be expected, and adhesion to a base film can be improved. The polycarboxylic acid anhydride is not particularly limited, and examples thereof include aromatic acids such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, ethylene glycol bis (dehydrated trimellitate), and glycerol dehydrated trimellitate Polybasic carboxylic acid anhydrides; aliphatic polycarboxylic anhydrides such as fumaric anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, dodecenyl succinic anhydride; hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride Isoalicyclic polycarboxylic anhydride. These can be used alone or in combination of two or more.

Among the aforementioned polycarboxylic acid anhydrides, the aromatic polycarboxylic acid anhydride is more preferable than the aliphatic polycarboxylic acid anhydride and the alicyclic polycarboxylic acid anhydride because the former has a higher acid value or branch imparting effect, and is therefore preferred. Among them, trimellitic anhydride, ethylene glycol bis (dehydrated trimellitate), and glycerol dehydrated trimellitate are preferred. From the viewpoint of availability, trimellitic anhydride is more preferable.

The method for imparting a branch is not particularly limited, and there are those in which a trifunctional or higher polycarboxylic acid anhydride is used as a copolymerization component of the amorphous polyester resin (A) and polymerized together with other polycarboxylic acids and polyols through a dehydration and esterification step. method. As for the copolymerization amount of the polycarboxylic acid anhydride, when the total amount of the carboxylic acid component of the amorphous polyester resin (A) is 100 mol%, it is preferably 0.1 mol% or more, and more preferably 0.5 mol% or more. . If it is too small, the branch may be insufficiently provided. Also, it is preferably 5 mol% or less, more preferably 2 mol% or less, and even more preferably 1 mol% or less. If it is too large, mechanical properties such as a film may be reduced, and gelation may occur during polymerization.

The method of imparting an acid value is not particularly limited, and examples thereof include polymerization of a dicarboxylic acid component and a diol component into a polyester resin (prepolymer), and the addition of a trifunctional or higher polyvalent carboxylic acid anhydride into the system to impart an acid value. method. As for the copolymerization amount of the polycarboxylic acid anhydride, it is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, relative to the total amount of the carboxylic acid component of the polyester resin (prepolymer). If it is too small, the acid value may sometimes be insufficient. Also, it is preferably 5 mol% or less, more preferably 2 mol% or less, and even more preferably 1 mol% or less. If it is too large, mechanical properties such as a film may be reduced, and gelation may occur during polymerization.

The acid value of the amorphous polyester resin (A) is only required to be 5 equivalents / 10 ⁶ g or more, preferably 10 equivalents / 10 ⁶ g or more, and more preferably 15 equivalents / 10 ⁶ g or more. If it is too small, the reactivity with the polyisocyanate (C) may be reduced, and the adhesion may be reduced. On the other hand, it is required to be 400 equivalents / 10 ⁶ g or less, preferably 200 equivalents / 10 ⁶ g or less, more preferably 150 equivalents 10 ⁶ g or less, and even more preferably 130 equivalents 10 ⁶ g or less. If it is too much, hydrolysis will easily occur.

The amorphous polyester resin (A) is preferably one having two or more carboxyl groups at the end of the resin. Since the terminal of the amorphous polyester resin (A) has two or more carboxyl groups, the reactivity with polyisocyanate (C) can be improved compared to the case of one carboxyl group, and excellent adhesiveness can be exhibited.

The polyol component constituting the amorphous polyester resin (A) used in the present invention is not particularly limited, and examples thereof include aliphatic diols, aromatic diols, and alicyclic diols. In particular, aliphatic diols are preferably used.

The aliphatic diol may be any of a linear aliphatic diol and a branched aliphatic diol. The aliphatic diol is not particularly limited, and is preferably a diol having 2 to 12 carbon atoms. The more preferable carbon number of the aliphatic diol is 3 or more. Preferably, the number of carbons is 9 or less, the number of carbons is 8 or less, the number of carbons is 7 or less, and the number of carbons is 6 or less. As for the copolymerization amount of the aliphatic diol, when the total amount of the polyol component is 100 mol%, it is preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably 60 mol% or more. It is more preferably 70 mol% or more, particularly preferably 80 mol% or more, most preferably 90 mol% or more, and 100 mol%. If it is too small, the adhesion to a polyethylene terephthalate film (hereinafter, also referred to as a PET film) may be reduced.

Specific examples of the aliphatic diol are not particularly limited, and examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 2 -Methyl-1,3-propanediol, neopentyl glycol, methylpentanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decane Alkanediol, dodecanediol, etc. can be used alone or in combination of two or more kinds. Among them, ethylene glycol, neopentyl glycol, 1,4-butanediol, and 2-methyl-1,3-propanediol are particularly preferably used.

The alicyclic diol is not particularly limited, and examples thereof include cyclohexanediol, cyclohexanedimethanol, and hydrogenated xylene glycol. The aromatic diol is not particularly limited, and examples thereof include xylene glycol.

The glass transition temperature (hereinafter, also referred to as Tg) of the amorphous polyester resin (A) needs to be 20 ° C or lower. The glass transition temperature is preferably 14 ° C or lower, more preferably 13 ° C or lower, and even more preferably 12 ° C or lower. If the glass transition temperature is too high, the adhesion may decrease. The lower limit is not particularly limited, but is preferably -10 ° C or more, and more preferably -5 ° C or more.

The glass transition temperature in the present invention is measured by a differential scanning calorimeter (SII, DSC-200). Specifically, about 5 mg of a sample (sample) is placed in an aluminum stopper-type container and sealed, cooled to -50 ° C using liquid nitrogen, and then heated to 150 ° C at 20 ° C / minute. In the endothermic curve obtained in this process, the temperature at the intersection of the baseline before the endothermic peak appears and the tangent to the endothermic peak is taken as the glass transition temperature (Tg, unit: ° C).

The number average molecular weight of the amorphous polyester resin (A) needs to be 5,000 or more, preferably 6,000 or more, more preferably 7,000 or more, particularly preferably 8,000 or more, and particularly preferably 10,000 or more. It should be 40,000 or less, preferably 35,000 or less, more preferably 30,000 or less, and particularly preferably 25,000 or less. If the number average molecular weight is less than 5000, there may be insufficient mechanical properties as an adhesive, and sufficient adhesion to a substrate such as a polyethylene terephthalate film (hereinafter, also referred to as a PET film) may not be obtained. In the case of adhesiveness, processability, and heat and humidity resistance. If the number-average molecular weight is higher than 40,000, when the adhesive is dissolved in a solvent and used, the solution viscosity may become too high, which may cause problems such as practical use.

The polyester resin (A) used in the present invention is an amorphous polyester resin. Since it is amorphous, it can be stably dissolved in various organic solvents rather than crystalline. In addition, it is advantageous to consider the fact that after the adhesive composition is applied to the substrate, crystallization of the polyester resin does not occur, and adhesion strength is not reduced due to volume shrinkage. In the present invention, amorphous refers to a differential scanning calorimeter (DSC), which is heated from -100 ° C to 300 ° C at 20 ° C / min, and then cooled to -100 ° C at 50 ° C / min, and then at 20 ° C. / min was raised from -100 ° C to 300 ° C, and no melting peaks were displayed during the second heating process. Conversely, crystallinity refers to those who show a clear melting peak during any heating process.

<Amorphous Polyurethane Resin (B)> The amorphous polyurethane resin (B) used in the present invention is preferably a diol component and a diisocyanate component as a copolymerization component. Moreover, you may copolymerize a diamine component etc. as needed. The diol component is preferably one having a polyester polyol as a main component (50% by mass or more). Acrylic polyol, polyether polyol, etc. can also be used as a main component.

As the polyester polyol, the aforementioned amorphous polyester resin (A) can be used. Examples of the acid component of the polyester polyol include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids exemplified in the aforementioned amorphous polyester resin (A). Among them, an aromatic dicarboxylic acid is preferably used, more preferably terephthalic acid and / or isophthalic acid.

In terms of the copolymerization amount of the aromatic dicarboxylic acid, when the total amount of the carboxylic acid component is 100 mol%, it is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol%. Above, especially preferred is 95 mol% or more, and 100 mol% is not a problem. If it is too small, the humidity and heat resistance may decrease.

Examples of the diol component of the polyester polyol include aliphatic diols, aromatic diols, and alicyclic diols exemplified in the aforementioned amorphous polyester resin (A). Among them, aliphatic diols are preferred, and ethylene glycol and / or neopentyl glycol are more preferred.

As for the copolymerization amount of the aliphatic diol, when the total amount of the polyol component is 100 mol%, it is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more. Especially good is 95 mol% or more, 100 mol% is OK.

The diol component may contain a low-molecular-weight component other than the polyester polyol, if necessary, without any problem. Examples of the diol compound include 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 2 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentane Alkanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2 ', 2'-dimethyl-3-hydroxypropionate, 2 -N-butyl-2-ethyl-1,3-propanediol, 3-ethyl-1,5-pentanediol, 3-propyl-1,5-pentanediol, 2,2- Diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol, 3-phenyl-1,5-pentanediol, 2,5-dimethyl-3- Sodium sulfo-2,5-hexanediol and the like. Also, for example, 1,2-propanediamine, 1,5-pentamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, and 1,2-diaminocyclobutane can be used. , 1,2-diaminocyclopentane, 1,2-diaminocycloheptane and other diamine compounds. One or two or more of these low molecular weight components can be used. Among them, neopentyl glycol is preferred.

The diol component preferably contains 50% by mass or more of the polyester polyol, more preferably 60% by mass or more, and even more preferably 70% by mass or more. If it is too small, there is a case where the urethane group concentration becomes high and the cohesive force is obtained, and the adhesiveness with the substrate may be deteriorated. The content is preferably 99% by mass or less, and more preferably 98% by mass or less. If it is too much, the concentration of the urethane group may decrease, the cohesive force may decrease, and the adhesion strength may decrease.

When using the said amorphous polyester resin (A) as a diol component, it is preferable that it is an acid addition without using a polycarboxylic acid anhydride. When acid addition is carried out, a resin terminal may have a carboxylic acid group, and the reactivity with a diisocyanate component may fall.

The diisocyanate component used in the amorphous polyurethane resin (B) is not particularly limited, and examples thereof include an aromatic diisocyanate component, an aliphatic diisocyanate component, and an alicyclic diisocyanate component. Examples of the aromatic diisocyanate component include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, terephthalic acid diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, and 3,3'-dimethoxyl. -4,4'-biphenylphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 4,4'-diisocyanate diphenyl ether, 1,5-xylene diisocyanate, or O-tolidine diisocyanate and the like. Examples of the aliphatic diisocyanate component include ethylene diisocyanate, propylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, or 3,3'-dimethylbiphenyl-4,4 ' -Diisocyanates and the like. Examples of the alicyclic diisocyanate include 1,3-diisocyanate methylcyclohexane, 1,4-diisocyanate methylcyclohexane, isophorone diisocyanate, and the like. One or more of these may be used. Among them, an aromatic diisocyanate component is preferable, and diphenylmethane diisocyanate is more preferable.

The number average molecular weight of the amorphous polyurethane resin (B) needs to be 5,000 or more, preferably 6,000 or more, more preferably 7,000 or more, particularly preferably 8,000 or more, and particularly preferably 10,000 or more. It should be 60,000 or less, and preferably 50,000 or less. If the number average molecular weight is less than 5,000, the mechanical properties as an adhesive may be insufficient, and sufficient adhesion, processability, and heat and humidity resistance to substrates such as PET films may not be obtained. If the number-average molecular weight is higher than 60,000, the viscosity of the solution may become too high when the adhesive is dissolved in a solvent and used, which may cause problems such as practical use.

The glass transition temperature of the amorphous polyurethane resin (B) needs to be 50 ° C or higher. More preferably, the glass transition temperature is 60 ° C or higher, particularly preferably 70 ° C or higher. If the glass transition temperature is too low, blocking may occur. The temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower, and even more preferably 100 ° C or lower. If the glass transition temperature is too high, it may not be soluble in organic solvents.

The polyurethane resin (B) used in the present invention is an amorphous polyurethane resin. Since it is amorphous, it can be stably dissolved in various organic solvents rather than crystalline. In addition, it is advantageous in consideration of the fact that after the adhesive composition is applied to the substrate, crystallization of the polyurethane resin does not occur, and adhesion strength is not reduced due to volume shrinkage. In the present invention, amorphous refers to a differential scanning calorimeter (DSC), which is heated from -100 ° C to 300 ° C at 20 ° C / min, and then cooled to -100 ° C at 50 ° C / min, and then at 20 ° C. / min was raised from -100 ° C to 300 ° C, and no melting peaks were displayed during the second heating process. Conversely, crystallinity refers to those who show a clear melting peak during any heating process.

The amorphous polyurethane resin (B) used in the present invention may have an acid value. The method for introducing a carboxyl group into the amorphous polyurethane resin (B) used in the present invention includes a method of synthesizing an amorphous polyurethane using a polyester polyol that has been subjected to an acid modification treatment at the terminal. Method for ester resin; method for synthesizing amorphous polyurethane resin using dimethylolpropionic acid, dimethylolbutyric acid, etc. as chain extender. Among these, in the polymerization of the amorphous polyurethane resin, the latter is preferred in order to adjust the molecular weight to an appropriate level.

The content of the amorphous polyurethane resin (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass, and even more preferably 15 parts by mass based on 100 parts by mass of the amorphous polyester resin (A). the above. If it is too small, adhesion may occur. Moreover, it is preferably 70 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less. If it is too much, the adhesiveness may decrease.

<Polyisocyanate (C)> The polyisocyanate (C) used in the present invention is not particularly limited as long as it has two or more isocyanate groups in the molecule. In view of weather resistance, an aliphatic polyisocyanate is preferred. 5. Alicyclic polyisocyanate, preferably an aliphatic diisocyanate or an alicyclic diisocyanate. Specific examples of the polyisocyanate (C) are not particularly limited. Examples of the aliphatic polyisocyanate include ethylene diisocyanate, propylene diisocyanate, hexamethylene diisocyanate (hereinafter, also referred to as HDI), or tetramethylene. Methyl diisocyanate and the like. Examples of the alicyclic diisocyanate include 1,3-diisocyanate methylcyclohexane, 1,4-diisocyanate methylcyclohexane, and isophorone diisocyanate. Further, examples thereof include compounds obtained by polyfunctionalization using these, or compounds obtained by modifying a diol compound using the above isocyanate. Moreover, you may use an aromatic diisocyanate. Examples of the aromatic diisocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, terephthalic acid diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, and 3,3'-dimethoxy- 4,4'-biphenylphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4 '-Diisocyanate diphenyl ether, or 1,5-xylene diisocyanate. These can be used alone or in combination of two or more. Among them, as the aliphatic polyisocyanate compound, hexamethylene diisocyanate can be cited as an ideal example, and as the alicyclic polyisocyanate compound, isophorone diisocyanate can be cited as an ideal example.

The polyisocyanate (C) is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the polyester resin (A). It is more preferably 1 part by mass or more, particularly preferably 1.5 part by mass or more, and particularly preferably 2 part by mass or more. It is preferably 20 parts by mass or less, more preferably 19 parts by mass or less, particularly preferably 18 parts by mass or less, particularly preferably 17 parts by mass or less, and most preferably 16 parts by mass or less. If it is too small, there may be a case where the reaction with the amorphous polyester resin (A) is insufficient and the solvent resistance may decrease. If it is too much, the adhesiveness with the amorphous polyurethane resin (B) may be reduced.

<Adhesive composition> The adhesive composition of the present invention is a composition containing the aforementioned amorphous polyester resin (A), amorphous polyurethane resin (B), and polyisocyanate (C) . The adhesive composition can be blended widely as an additive user within a range that does not impair the characteristics of the present invention. The additives are not particularly limited, and examples thereof include well-known additives such as ultraviolet absorbers, antioxidants, silane coupling agents, plasticizers, and various adhesive resin components, and these may be contained alone or in combination of two or more. In addition, as long as the effect of the present invention is not impaired, a polyester resin different from the amorphous polyester (A) and a polyamine different from the amorphous polyurethane resin (B) are blended. Formate resins are also fine. It is also possible to further blend a polyolefin resin, a polyimide resin, a polyimide resin, a polyimide resin, and the like.

In order to control reactivity, a hardening catalyst may be used. The catalyst is not particularly limited, and preferably includes a catalyst for curing a polyisocyanate, and particularly preferably a catalyst for curing a polyisocyanate based on a tin or an amine. It is not particularly limited, and specific examples include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dibutyl maleate, dibutyltin dibutyl maleate, and dibutyltin dibutyl maleate. Tin catalysts such as ethoxylated stannoxanes; tributylamine, triethylenediamine, N'-methyl-N- (2-dimethylaminoethyl) piper , 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -non-5-ene, 6-dibutyl Amine catalysts such as amine-1,8-diazabicyclo (5,4,0) -7-undecene and 1,2-dimethylimidazole. In particular, when it is combined with a free polyisocyanate, it is preferably obtained by forming a salt of the tertiary amine compound using phenol or the like.

The adhesive composition of the present invention can also be made into a varnish by containing an organic solvent. The organic solvent is not particularly limited as long as it dissolves the amorphous polyester resin (A), the amorphous polyurethane resin (B), and the polyisocyanate (C). Specifically, for example, aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; cyclohexane, cyclohexene, methylcyclohexane, Cycloaliphatic hydrocarbons such as ethyl cyclohexane; N, N-dimethylformamide (DMF), dimethyl sulfenamide (DMSO), N, N-dimethylacetamide (DMAc), N- Aprotic polar solvents such as methyl-2-pyrrolidone (NMP); alcohol solvents such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, propanediol, and phenol; acetone, methyl isobutanone , Methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone and other ketone solvents; methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate and other ester solvents, One of these can be used or two or more can be used. In view of the solubility of the resin, it is particularly preferable to contain a part of the aprotic polar solvent. By containing an aprotic polar solvent, the resins are easily mixed with each other in the solvent, and the compatibility is improved, whereby the coating film is less likely to cause streaks. Particularly preferred is N, N-dimethylformamide (DMF).

The organic solvent is preferably 50 parts by mass or more with respect to 100 parts by mass of the amorphous polyester resin (A), more preferably 80 parts by mass or more, and even more preferably 100 parts by mass or more. If it is too small, application to the substrate may become difficult. In addition, it is preferably 1,000 parts by mass or less, more preferably 900 parts by mass or less, and even more preferably 800 parts by mass or less. If it is too much, it may become disadvantageous in terms of manufacturing cost and transportation cost. In addition, a part of the organic solvent preferably contains an aprotic polar solvent, and is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, based on 100 parts by mass of the amorphous polyester resin (A). The content is preferably 100 parts by mass or less, and more preferably 70 parts by mass or less.

<Adhesive layer> An adhesive layer can be produced using the adhesive composition of this invention. The adhesive layer of the present invention refers to a layer of the adhesive composition after the aforementioned adhesive composition is coated on a substrate, dried, and cured by curing. The film thickness of the adhesive layer is preferably 4 μm or more, and more preferably 5 μm or more. If it is too thin, the effect as an adhesive may not be exhibited in some cases. The thickness is preferably 30 μm or less, and more preferably 25 μm or less.

<Laminated body> The laminated body of the present invention refers to the two-layer laminated body (substrate 1 / adhesive agent layer) of the above-mentioned adhesive agent layer and substrate 1, or a substrate bonded to the surface of the adhesive agent layer. 3 laminated layer (base material 1 / adhesive layer / base material 2) obtained from material 2 and a laminated body (base material 1 / adhesive layer layer) obtained by further laminating 2 laminated layers to the 3 laminated layer body / Substrate 2 / adhesive layer / substrate 3).

The substrate 1, substrate 2 and substrate 3 which can be used in the present invention are not particularly limited, and examples thereof include metal, plastic, wood, cloth, and paper. The metal material is not particularly limited, and examples thereof include various metals such as aluminum, SUS, copper, iron, and zinc, and respective alloys, metal plates such as plated products, metal foils, and vapor-deposited layers. The plastic is not particularly limited, and examples thereof include a plastic sheet or a plastic film such as polyvinyl chloride, polyester, polyolefin, polyamide, polyvinyl alcohol, or polyurethane. The cloth is not particularly limited, and examples thereof include cotton, silk, and linen, and other examples include synthetic fibers such as polyester. The paper is not particularly limited, and examples thereof include high-quality paper, kraft paper, paper rolls, and cellophane. The aforementioned substrate 1, substrate 2 and substrate 3 may be the same type or different types. A plurality of substrates selected from these may be laminated.

The adhesive composition of the present invention is particularly suitable for polishing pad applications. In the case of a polishing pad, the substrate 1 should be a plastic film, and more preferably a polyester film. In a polishing pad, an adhesive composition can be applied to a polyester film, dried, and cured by curing or the like to produce a laminate. Then, a polyurethane prepolymer solution is applied to the surface of the adhesive layer of the laminate, and then wet-coagulation and drying (wet film formation) are performed to produce a porous film on the polyester film. Polishing pad for urethane polishing layer (polyester film / adhesive layer / porous urethane polishing layer). [Example]

Hereinafter, examples are described in order to explain the present invention in more detail, but the present invention is not limited to the examples. In addition, the part abbreviated in an Example means a mass part.

<Production Example (a-1) of Polyester Resin (A)> In a reaction vessel provided with a thermometer, a stirrer, a reflux cooling tube, and a distillation tube, 49.8 parts of terephthalic acid, 49.8 parts of isophthalic acid, and Tetra-n-butyl titanate as a catalyst is 58.4 parts of diacid, 35.4 parts of ethylene glycol, 69.3 parts of neopentyl glycol, 60.0 parts of 1,4-butanediol, and 0.03 mole% of the total acid content. (Hereinafter, sometimes abbreviated as TBT), a transesterification reaction was performed while increasing the temperature from 160 ° C to 240 ° C over 4 hours. Then, the inside of the system was gradually depressurized, and the pressure was reduced to 5 mmHg over 20 minutes, and a polycondensation reaction was further performed at 260 ° C for 90 minutes under a vacuum of 0.3 mmHg or less. The mixture was cooled to 220 ° C. under a stream of nitrogen, and 2 parts of trimellitic anhydride was charged and reacted for 30 minutes to obtain a polyester resin (a-1). The results of the obtained polyester resin (a-1) are shown in Table 1.

Production Examples of Polyester Resin (a-2) to (a-11) In accordance with Production Example of Polyester Resin (a-1), the polyester resin (a-2) was produced by changing the type of raw materials and blending ratio. ~ (A-11). The results are shown in Table 1. In addition, a resin having a number average molecular weight of 50,000 was gelled during the manufacturing process, so it could not be manufactured.

【Table 1】

1. Composition of polyester resin (A) The composition and composition ratio of polyester resin (A) are determined by performing ¹ H-NMR measurement (protonic nuclear magnetic resonance spectrometry) at a resonance frequency of 400 MHz. As a measuring device, a 1H-NMR device 400-MR manufactured by Varian was used, and as a solvent, deuterated chloroform was used.

2. Glass transition temperature (Tg) was measured with a differential scanning calorimeter (manufactured by SII, DSC-200). The sample was obtained by putting 5 mg of a sample (polyester resin or polyurethane resin) in an aluminum stopper-type container and sealing it. First, the sample was cooled to -50 ° C using liquid nitrogen, and then heated to 150 ° C at 20 ° C / minute. In the endothermic curve obtained in this process, the temperature at the intersection of the baseline before the endothermic peak appears and the tangent to the endothermic peak is taken as the glass transition temperature (Tg, unit: ° C).

3. Acid value (AV) Accurately weigh 0.2 g of the sample (polyester resin or polyurethane resin) and dissolve it in 40 ml of chloroform, and titrate with 0.01-N potassium hydroxide in ethanol solution. As an indicator, phenolphthalein was used. The measured value is converted into an equivalent weight per 10 ⁶ g sample, and the unit is equivalent weight / 10 ⁶ g.

4. Number average molecular weight (Mn) The sample (polyester resin or polyurethane resin) is dissolved in tetrahydrofuran or diluted with tetrahydrofuran so that the resin concentration becomes about 0.5%, and polytetrafluoroethylene with a pore diameter of 0.5 μm will be used. A membrane filter was used as a sample for measurement. The molecular weight of the sample for measurement was measured using a gel permeation chromatography using tetrahydrofuran as a mobile phase and a differential refractometer as a detector. The flow rate was set to 1 mL / min, and the column temperature was set to 30 ° C. KF-802, 804L, and 806L manufactured by Showa Denko were used for the column. The molecular weight standard uses monodisperse polystyrene. However, when the measurement sample is not dissolved in tetrahydrofuran, N, N-dimethylformamide is used instead of tetrahydrofuran. Low-molecular compounds (oligomers, etc.) having a number-average molecular weight of less than 1,000 are not included in the count and are omitted.

In Table 1, the copolymerization components of the polyester resin are represented by the following abbreviations. TPA: terephthalic acid residue IPA: isophthalic acid residue AA: adipic acid residue SA: sebacic acid residue TMA: trimellitic acid residue EG: ethylene glycol residue 2MG: 2-formaldehyde -1,3-propanediol residue NPG: neopentyl glycol residue BD: 1,4-butanediol residue

<Synthetic Example (b-1) of Amorphous Polyurethane Resin (B)> In a reaction tank equipped with a stirrer, a thermometer, and a Dimroth cooling tube, a polyester polyol (composed of p-benzene Dicarboxylic acid / isophthalic acid // ethylene glycol / neopentyl glycol = 50/50 // 50/50 mole ratio, number average molecular weight 2000, glass transition temperature 55 ° C) 220 parts, 200 parts toluene, warmed to Dissolve completely at 80 ° C over 1 hour. Thereafter, 150 parts of methyl ethyl ketone, 8 parts of neopentyl glycol, 3 parts of 1,6-hexanediol, and 50 parts of 4,4′-diphenylmethane diisocyanate were added, and the mixture was stirred at 80 ° C. for 1 hour. Then, 0.1 g of dibutyltin dilaurate was added, and it stirred at 80 degreeC for 10 hours, and the urethanation reaction was performed. After completion of the reaction, toluene and methyl ethyl ketone were added and diluted to obtain a solution of a target amorphous polyurethane resin (B) having a solid content concentration of 32% by mass. The characteristic value of the amorphous polyurethane resin (B) obtained in this way is a number average molecular weight of 26,000, a glass transition temperature of 80 ° C, and an acid value of 1 equivalent / 10 ⁶ g or less.

<Synthetic Example (b-2) of Amorphous Polyurethane Resin (B)> In a reaction tank equipped with a stirrer, a thermometer, and a Dairy cooling tube, a polyester polyol (composing terephthalic acid / Isophthalic acid / ethylene glycol / sebacic acid / neopentyl glycol = 50/45/5 // 50/50 mole ratio, number average molecular weight 2000, glass transition temperature 55 ° C) 220 parts, toluene 200 parts The temperature was raised to 80 ° C, and the solution was completely dissolved in 1 hour. Thereafter, 150 parts of methyl ethyl ketone, 8 parts of neopentyl glycol, 3 parts of 1,6-hexanediol, and 50 parts of 4,4′-diphenylmethane diisocyanate were added, and the mixture was stirred at 80 ° C. for 1 hour. Then, 0.1 g of dibutyltin dilaurate was added, and it stirred at 80 degreeC for 10 hours, and the urethanation reaction was performed. After completion of the reaction, toluene and methyl ethyl ketone were added and diluted to obtain a solution of a target amorphous polyurethane resin (B) having a solid content concentration of 32% by mass. The characteristic value of the amorphous polyurethane resin (B) obtained in this way is a number average molecular weight of 42,000, a glass transition temperature of 60 ° C., and an acid value of 1 equivalent / 10 ⁶ g or less.

<Example 1> 70 parts of amorphous polyester resin (a-1), 20 parts of methyl ethyl ketone, and 20 parts of toluene were added to a reaction container provided with a thermometer, a stirrer, and a reflux cooling tube, and dissolved. Thereafter, 125 parts (30 parts of solids) of the amorphous polyurethane resin (b-1) solution and 25 parts of DMF were added and dissolved. One part of polyisocyanate (c-1) was added to this solution, and the adhesive composition 1 was obtained. The results are shown in Table 2.

<Examples 2 to 11 and Comparative Examples 1 to 5> According to Example 1, the types and blending ratios of the raw materials were changed to produce adhesive compositions 2 to 16. In Tables 2 and 3, the following materials were used for the polyisocyanate (C). Polyisocyanate (c-1): HDI isocyanurate "CORONATE (registered trademark) HX manufactured by Nippon Polyurethane Industry" Polyisocyanate (c-2): HDI addition object "CORONATE (registered trademark) HL manufactured by Nippon Polyurethane Industry" "

【Table 2】

【table 3】

5. Evaluation of coatability The adhesive composition was applied to a PET film having a thickness of 50 μm by an applicator so that the film thickness after drying was 25 μm. It was confirmed whether streaks were generated when the adhesive composition was applied by an applicator. Evaluation Criteria ○: No streak △: Slightly streaked ×: Streaked

6. Blocking resistance The adhesive composition was applied to a PET film having a thickness of 50 μm so that the film thickness after drying was 25 μm, and dried at about 120 ° C. for about 1 minute to prepare a test sample. Two test samples were prepared, and the adhesive layers were overlapped with each other. After pressing at 40 ° C and 30 MPa for 5 minutes, the presence or absence of adhesion was confirmed. Evaluation Criteria ○: No blocking ×: Blocking

7. Solvent resistance The adhesive composition was applied to a PET film having a thickness of 50 μm so that the film thickness after drying was 25 μm. Then, it was made to dry at about 120 degreeC for about 1 minute, and the solvent was volatilized. After that, aging was performed at 40 ° C for 3 days. A urethane prepolymer solution prepared in advance was applied to the adhesive layer to obtain a wet film. The cross section was cut out, and the presence or absence of peeling was visually confirmed. In addition, the urethane prepolymer solution is a dimethyl formamide with polybutylene adipate diol / diphenylmethane-4,4'-diisocyanate / diethylene glycol as a copolymerization component. DMF solution of ester prepolymer. Evaluation Criteria ○: No peeling △: Partial peeling ×: All peeling

8. Adhesive strength The adhesive composition was applied to a PET film having a thickness of 50 μm so that the film thickness after drying was 25 μm. Then, it was made to dry at about 120 degreeC for about 1 minute, and the solvent was volatilized. After that, aging was performed at 40 ° C for 3 days. A urethane prepolymer solution prepared in advance was laminated on this adhesive layer by wet film formation so that the film thickness after drying was 25 μm. At this time, a partial peeling margin is made. Then, the adhesive strength was measured. Those exhibiting a strength above 1kgf / inch have good adhesion strength.

Claims (6)

An adhesive composition comprising: an amorphous polyester resin (A) having a number average molecular weight of 5,000 to 40,000, a glass transition temperature of 20 ° C or lower, and an acid value of 5 to 400 equivalents / 10 ⁶ g; An amorphous polyurethane resin (B) having a glass transition temperature of 50 ° C. or higher and a polyisocyanate (C) of 5000 to 60,000. For example, the adhesive composition according to item 1 of the patent application scope, wherein the amorphous polyester resin (A) has two or more carboxyl groups at the end of the resin. For example, the adhesive composition according to item 1 or 2 of the patent application range, wherein the blend ratio of the amorphous polyester resin (A) and the amorphous polyurethane resin (B) is relative to that of the amorphous 100 parts by mass of the polyester resin (A), and 5 to 70 parts by mass of the amorphous polyurethane resin (B). A laminated body is obtained by laminating an adhesive layer composed of an adhesive composition according to any one of claims 1 to 3 and a plastic film. A laminated body is obtained by laminating a resin on the surface of the adhesive layer of the laminated body such as the fourth item of the patent application. A polishing pad is provided with a polishing layer in a part of a laminated body such as the item 5 of the patent application.