JP2013245312A - Composition for adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for adhesives having tough adhesive force, maintaining the adhesive force for a long time and keeping good appearance after curing.SOLUTION: There is provided a composition for adhesives containing a polyester polyol (a), a polycarbonate diol (b) and a polyisocyanate (c), wherein the component (b) is a polycarbonate diol having a repeating unit expressed by formula (A) and terminal hydroxyl group, 60-100 mol% of the repeating unit expressed by formula (A) has 5 (B) and 6 (C) carbons, the ratio of (B) and (C) is 70:30 to 30:70 (molar ratio) and the ratio of primary terminal OH is 95-99.5%. In the formula, R is 2-15C bivalent aliphatic or alicyclic hydrocarbon group.

Description

  The present invention relates to an adhesive composition.

  Polyurethane adhesives can be designed for a wide range of physical properties, forms, and curing modes by selecting their constituent components, and are also excellent in chemical properties such as chemical resistance. It is used for bonding many substrates such as wood. Among them, adhesives for lamination films for flexible packaging used for food packaging bags that require flexibility and retort resistance (see, for example, Patent Document 1), and high durability such as hydrolysis resistance and heat resistance. Is used for an adhesive for automobile parts (for example, see Patent Document 2). In recent years, it has attracted attention as an adhesive for a solar cell back surface sealing sheet that is required to maintain adhesive strength over a long period of time (see, for example, Patent Documents 3 and 4).

JP 2004-285183 A JP 2011-195840 A JP 2008-4691 A JP 2011-213939 A

  However, when the reactivity of the polyol used is low, not only the curing time is lengthened, but also the unreacted polyol remains, resulting in inconveniences such as reduced adhesion and bleeding of the unreacted polyol. . In addition, when a highly crystalline raw material is used, inconveniences such as whitening of the adhesive layer also occur. Therefore, there is a demand for a polyurethane-based adhesive that has good adhesiveness, can maintain adhesive strength over a long period of time, and has flexibility. Furthermore, there is a demand for an adhesive that is transparent and hardly colored without turbidity, spots, or bleed-out.

  The present invention has been made in view of the above problems, and has an adhesive composition that has a tough adhesive force, can maintain the adhesive force over a long period of time, and can maintain an excellent appearance after curing. The purpose is to provide.

As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by using a specific polycarbonate diol, and has led to the present invention.
That is, the configuration of the present invention is as follows.

[1]
Containing polyester polyol (a), polycarbonate diol (b), and polyisocyanate (c);
The polycarbonate diol (b) is a polycarbonate diol having a repeating unit represented by the following formula (A) and a terminal hydroxyl group,
60 to 100 mol% of the repeating unit represented by the following formula (A) is a repeating unit represented by the following formula (B) and the following formula (C),
The ratio of the repeating unit represented by the following formula (B) and the repeating unit represented by the following formula (C) is 70:30 to 30:70 (molar ratio),
The primary terminal OH ratio is 95 to 99.5%.
Adhesive composition.
(In the formula, R represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 15 carbon atoms.)
[2]
The composition for adhesives according to [1] above, wherein the number average molecular weight of the polycarbonate diol (b) is 450 to 1250.

  INDUSTRIAL APPLICABILITY The present invention has an effect that it can provide an adhesive composition having a tough adhesive force and capable of maintaining the adhesive force over a long period of time and maintaining a good appearance after curing.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[Adhesive composition]
The composition for adhesives of this embodiment contains a polyester polyol (a), a polycarbonate diol (b), and a polyisocyanate (c),
The polycarbonate diol (b) is a polycarbonate diol having a repeating unit represented by the following formula (A) and a terminal hydroxyl group,
60 to 100 mol% of the repeating unit represented by the following formula (A) is a repeating unit represented by the following formula (B) and the following formula (C),
The ratio of the repeating unit represented by the following formula (B) and the repeating unit represented by the following formula (C) is 70:30 to 30:70 (molar ratio),
The primary terminal OH ratio is 95 to 99.5%. Hereinafter, the present invention will be specifically described.
(In the formula, R represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 15 carbon atoms.)

[Polyester polyol (a)]
The polyester polyol (a) used in the present embodiment is not particularly limited. Specifically, the polyester polyol (a) can be obtained by an esterification reaction using dicarboxylic acid and glycol as raw materials. Although it does not specifically limit as dicarboxylic acid, Specifically, a succinic acid, glutaric acid, adipic acid, pimelic acid, spellic acid, mazeline acid, sebacic acid, brassic acid, 1, 4- cyclohexane dicarboxylic acid, 1,3 -Aliphatic or alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer acid, hydrogenated dimer acid; isophthalic acid, terephthalic acid, Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid can be mentioned, and one or more can be selected and used. Moreover, dicarboxylic acid can be used for superposition | polymerization in the state of ester derivatives, such as the anhydride or dimethyl ester. Although it does not specifically limit as glycol, Specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butane Diol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane di Fats such as methanol, tricyclodecane dimethanol, 1,9-nonanediol, 2-methyloctanediol, 1,10-dodecanediol, 2-butyl-2-ethyl-1,3-propanediol, polyoxymethylene glycol Group or alicyclic glycols, one or two It can be selected and used more.

In this embodiment, 1 type (s) or 2 or more types can be selected and used from the polyester polyol (a) polymerized using said raw material. Among them, it is preferable to use the polyester polyol (a) having low crystallinity because it is possible to avoid whitening of the adhesive layer over time. Here, the term “low crystallinity” means having no melting point near room temperature.
In the esterification reaction, a known reaction catalyst can be used.

  In this embodiment, the molecular weight of the polyester polyol (a) is not particularly limited, but specifically, the number average molecular weight is preferably 5,000 to 50,000. If the molecular weight is 5,000 or more, the initial cohesive force is high and does not cause delamination, and if it is less than 50,000, there may be a problem in coatability due to the high viscosity of the adhesive. Absent. Moreover, it is more preferable that it is 10,000-35,000 from this viewpoint. The number average molecular weight of the polyester polyol (a) can be measured by a method using gel permeation chromatography (GPC).

[Polycarbonate diol (b)]
The polycarbonate diol (b) used in the present embodiment is a polycarbonate diol having a repeating unit represented by the following formula (A) and a terminal hydroxyl group, and 60 to 100 of the repeating unit represented by the following formula (A). The mol% is a repeating unit represented by the following formula (B) and the following formula (C), and the ratio of the repeating unit represented by the following formula (B) and the repeating unit represented by the following formula (C) is: 70:30 to 30:70 (molar ratio), and the primary terminal OH ratio is 95 to 99.5%.

In the polycarbonate diol (b), the proportion of the repeating unit represented by the following formula (A) is preferably 95 mol% or more and 100 mol% or less, more preferably 97 mol% or more and 100 mol% or less, and still more preferably. It is 99 mol% or more and 100 mol% or less.
(In the formula, R represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 15 carbon atoms.)

(Primary terminal OH ratio)
The primary terminal OH ratio of the polycarbonate diol (b) in this embodiment is an alcohol obtained as an initial fraction by heating the polycarbonate diol at a temperature of 160 ° C. to 200 ° C. with stirring under a pressure of 0.4 kPa or less. In the class, it is defined as the mass% of the diol having a primary hydroxyl group at both ends with respect to the total of alcohols (excluding ethanol) containing the diol. The alcohol containing diol here corresponds to the segment of the terminal portion of polycarbonate diol (b). Specifically, the primary terminal OH ratio in the present embodiment is such that the polycarbonate diol (70 g to 100 g) is heated at a temperature of 160 ° C. to 200 ° C. with stirring under a pressure of 0.4 kPa or less. A fraction corresponding to about 1 to 2% by weight of the diol, i.e. about 1 g (0.7 to 2 g) of the initial fraction, was obtained, using about 100 g (95 to 105 g) of ethanol as the solvent. The value calculated by the following formula (1) from the value of the peak area of the chromatogram obtained by collecting the collected solution and subjecting the collected solution to gas chromatography (GC) analysis.
Primary terminal OH ratio (%) = A ÷ B × 100 (1)
A: Sum of peak areas of diols whose both ends are primary OH groups B: Sum of peak areas of alcohols (excluding ethanol) containing diols

  The “alcohol containing diol (excluding ethanol)” detected in the GC analysis performed for the measurement of the primary terminal OH ratio is not particularly limited, but specifically, 1,5- Pentanediol, 1,6-hexanediol, 1,4-butanediol, 1,5-hexanediol, 1,4-cyclohexanediol, 1,4-pentanediol, 1-butanol, 1-pentanol, 1-hexanol Etc. When the polycarbonate diol is heated at a temperature of 160 ° C. to 200 ° C. with stirring under a pressure of 0.4 kPa or less as described above, only the terminal portion of the polycarbonate diol (b) is decomposed into alcohol units containing the diol and evaporated. And obtained as a fraction. The ratio of the diol in which both ends of all the alcohols in this fraction are primary OH groups is defined as the primary terminal OH ratio of the polycarbonate diol (b) in this embodiment.

  In the adhesive composition in the present embodiment, it is important to appropriately control the reactivity of the polycarbonate diol (b). If the primary terminal OH ratio is 95 to 99.5%, an appropriate adhesion time can be obtained. Moreover, it can avoid that polyester polyol (a) and polyisocyanate (c) react preferentially and become a non-uniform structure irrespective of the kind of polyisocyanate (c) and polyester polyol (a) to be used. Therefore, the adhesive strength is improved. Alternatively, there is an effect that a decrease in adhesive strength with time is small. Furthermore, the inconvenience of bleeding of unreacted polycarbonate diol and low molecular weight polyurethane can be avoided. Moreover, when the primary terminal OH ratio is 96% to 99.5%, it is preferable because the above effect is higher, and when it is 97% to 99.5%, it has an appropriate bonding time and has high bonding strength, It is more preferable because an adhesive composition with excellent balance can be obtained with little decrease in adhesive strength over time.

  The method for producing the polycarbonate diol (b) used in the present embodiment is not particularly limited. Specifically, various methods described in Schnell, Polymer Reviews Vol. 9, p9-20 (1994). Can be manufactured.

  The polycarbonate diol (b) used in this embodiment uses 1,5-pentanediol and 1,6-hexanediol as diol raw materials. Although it does not specifically limit as a compound which can be used in addition to these diols, Specifically, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,7-heptanediol, 1,8 -Diols having no side chain such as octanediol, 1,9-nonanediol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol; 2-methyl-1,8-octanediol 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4 -Diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3-propyl Examples include diols having side chains such as pan diol; cyclic diols such as 1,4-cyclohexanedimethanol and 2-bis (4-hydroxycyclohexyl) -propane. One or more diols are used as raw materials. May be. The amount is not particularly limited as long as the ratio of the repeating units shown in the present embodiment is satisfied.

  Furthermore, for the production of the polycarbonate diol (b) used in the present embodiment, if necessary, a compound having 3 or more hydroxyl groups per molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, etc. Can also be used. In addition, it is preferable that the said compound shall be 0.1-5 mass% with respect to the total amount of diol used as a raw material so that it may bridge | crosslink during the polymerization reaction of polycarbonate diol (b), and gelatinization may not occur. The amount of the compound when used is more preferably 0.1 to 2% by mass.

  Although it does not specifically limit as ester carbonate used in manufacture of the polycarbonate diol (b) used by this embodiment, Specifically, Dialkyl carbonates, such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate; Diphenyl carbonate, etc. And dialkyl carbonates such as ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate. Among these, one or more carbonic esters can be used as a raw material. The use of dialkyl carbonate and / or diaryl carbonate is preferable because the polycarbonate diol (b) satisfying the primary terminal OH ratio of this embodiment can be easily obtained depending on conditions such as the charging ratio of diol and carbonate. Moreover, it is more preferable to use dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and dibutyl carbonate from the viewpoint of easy availability and easy setting of conditions for the polymerization reaction.

  In the production of the polycarbonate diol (b) used in this embodiment, a catalyst may or may not be added. When adding a catalyst, it can select freely from a normal transesterification catalyst. Such a transesterification reaction catalyst is not particularly limited, and specifically, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, cobalt, germanium, tin, Metals such as lead, antimony, arsenic, and cerium, salts, alkoxides, and organic compounds are used. Particularly preferred are titanium, tin and lead compounds. Moreover, the usage-amount of a catalyst is 0.00001 to 0.1% of polycarbonate diol weight normally.

  As an example of the method for producing the polycarbonate diol (b), a method using dimethyl carbonate as the carbonate will be described. The production of the polycarbonate diol can be carried out in two stages. Diol and dimethyl carbonate are mixed at a molar ratio of 20: 1 to 1:10 and reacted at 100 to 300 ° C. under normal pressure or reduced pressure, and the resulting methanol is removed as a mixture with dimethyl carbonate to reduce the A molecular weight polycarbonate diol can be obtained. Next, heating at 160 to 250 ° C. under reduced pressure removes unreacted diol and dimethyl carbonate, and self-condenses the low molecular weight polycarbonate diol to obtain a polycarbonate diol having a predetermined molecular weight.

  The polycarbonate diol (b) having a predetermined primary terminal OH ratio is prepared by adding the diol and carbonate when the raw material diol purity, polymerization conditions such as temperature and time, and dialkyl carbonate and / or diaryl carbonate are used as the carbonate. It can be obtained by selecting one method from conditions such as a ratio, or by appropriately combining them.

  Industrially obtained 1,5-pentanediol generally contains 0.2 to 2% by mass of 1,5-hexanediol and 1,4-cyclohexanediol as impurities having secondary hydroxyl groups, respectively. doing. On the other hand, industrially obtained 1,6-hexanediol generally contains 0.1 to 2% by mass of impurities having a secondary hydroxyl group such as 1,4-cyclohexanediol. Since these diols having secondary hydroxyl groups have low transesterification reactivity during the production of polycarbonate diols, they often become terminal groups of polycarbonate diols, resulting in polycarbonate diols having secondary hydroxyl groups at the ends.

  In addition, when dialkyl carbonate and / or diaryl carbonate is used as the carbonate, polycarbonate is prepared by reacting the diol and carbonate in a stoichiometric amount or a proportion close to the stoichiometric amount corresponding to the molecular weight of the target polycarbonate diol. In many cases, an alkyl group or an aryl group derived from carbonate remains at the end of the diol. Therefore, by setting the amount of diol with respect to the carbonate to 1.01 to 1.30 times the stoichiometric amount, the terminal of the alkyl group or aryl group remaining at the terminal of the polycarbonate diol can be reduced to form a hydroxyl group. . Furthermore, due to a side reaction, the end of the polycarbonate diol becomes a vinyl group, or, for example, when dimethyl carbonate is used as the carbonate, it becomes a methyl ester or methyl ether. In general, the side reaction is more likely to occur as the reaction temperature is higher and the reaction time is longer. Then, it can suppress that the terminal of polycarbonate diol becomes a vinyl group by making reaction temperature into 200 degrees C or less, for example.

(Principal component ratio)
In the polycarbonate diol (b) used in the present embodiment, the ratio of the repeating units represented by the above formula (B) and the above formula (C) in the repeating units represented by the above formula (A) (hereinafter referred to as “main component”). The ratio is also referred to as 60 to 100 mol%. If the main component ratio is 60 mol% or more, it is preferable because a flexible adhesive layer can be obtained and the adhesive force hardly decreases with time. The case where a main component ratio is 70-100 mol% is more preferable, and the case where it is 85-100 mol% is still more preferable.

(Copolymerization ratio)
In the polycarbonate diol (b) used in the present embodiment, the ratio of the repeating unit represented by the above formula (B) and the repeating unit represented by the above formula (C) (hereinafter also referred to as “copolymerization ratio”), Formula (B): represented by the above formula (C)) is 70:30 to 30:70 in molar ratio. If the copolymerization ratio is within this range, a tough and flexible adhesive layer can be obtained without whitening over time, and the copolymerization ratio may be 65:35 to 35:65 in molar ratio. The case of 60:40 to 40:60 is more preferable.

  Conventionally, the polycarbonate diol (b) is composed of a repeating unit represented by the above formula (C) and a terminal hydroxyl group, and the polyurethane obtained by using the repeating unit has high crystallinity and is resistant to hydrolysis and heat. Although it was high, flexibility and adhesive strength were insufficient. Furthermore, the adhesive layer may be whitened over time. In the present embodiment, by including the repeating unit of the above formula (C) and the repeating unit (repeating unit of the above formula (B)) having an odd number of methylene chains, which has a methylene chain length close, does not have a branched structure. The crystallinity of the polycarbonate diol (b) can be reduced. Furthermore, by having a specific main component ratio and copolymerization ratio, the adhesive composition has both adhesive strength and flexibility while maintaining durability such as hydrolysis resistance and heat resistance, and hardly whitens over time. Can be obtained.

(Number average molecular weight)
The range of the number average molecular weight of the polycarbonate diol (b) used in the present embodiment is preferably 300 to 3000. When the number average molecular weight of the polycarbonate diol (b) is 300 or more, an adhesive composition having high adhesive strength and flexibility can be obtained. Moreover, if the number average molecular weight of polycarbonate diol (b) is 3000 or less, the viscosity of the composition for adhesives will not become high too much, and coating property will not fall. Furthermore, if the number average molecular weight of the polycarbonate diol (b) is 450 to 1250, compatibility with the polyester polyol is improved, uniformity of the adhesive composition is improved, and high adhesiveness is obtained. preferable. The number average molecular weight can be measured by the method described in Examples.

The polycarbonate diol (b) of the present embodiment may further include a structure represented by a repeating unit of the following formula (D) in the molecule for the purpose of improving the adhesive strength and flexibility.
(In the formula, R ₂ represents an alkylene group, and the alkylene group may be two or more types. X represents an integer of 2 or more.)

  In the polycarbonate diol (b) of the present embodiment, the content of the repeating unit of the formula (D) in the molecule is not particularly limited, but from the viewpoint of avoiding a decrease in heat resistance, the formula (A The repeating unit represented by the formula (D) (having an ether-derived structure) is preferably 0.05 to 5 mol% or less with respect to the carbonate repeating unit represented by More preferably, it is at most mol%.

  In this embodiment, it is preferable that the quantity of polycarbonate diol (b) is 5-95 mass% with respect to the sum total of polyester polyol (a) and polycarbonate diol (b). If this ratio is 5 mass% or more, the composition for adhesives which has a softness | flexibility and little adhesive strength fall with time is obtained. Moreover, if the said ratio is 95 mass% or less, the composition for adhesive agents which has high adhesive strength will be obtained. The ratio is more preferably 10 to 80%, and further preferably 15 to 60%.

  In addition, the composition for adhesives of this embodiment is comprised only by the polymer comprised only by the repeating unit represented by Formula (B), and / or the repeating unit represented by Formula (C). A polymer may be included.

[Polyisocyanate (c)]
The polyisocyanate (c) used in the present embodiment is not particularly limited as long as it has a plurality of isocyanate groups (including those that are blocked or modified). Specifically, 2,4-triresin diisocyanate, 2 , 6-triresin diisocyanate and mixtures thereof; MDI such as diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-2,2′-diisocyanate and mixtures thereof; naphthalene-1, NDI such as 5-diisocyanate; TODI such as 3,3′-dimethyl-4,4′-biphenylene diisocyanate; Crude TDI; PMDI such as polymethylene polyphenylene polyisocyanate; Aromatic diisocyanate such as crude MDI, 1,3-xylyl Range isocyanate XDI such as 1,4-xylylene diisocyanate and mixtures thereof; TMXDI such as 1,3-tetramethylxylylene diisocyanate, 1,4-tetramethylxylylene diisocyanate and mixtures thereof; aromatic aliphatic diisocyanates such as phenylene diisocyanate; 4 Hydrogenated MDI such as 2,4′-methylenebiscyclohexyl diisocyanate, 2,4′-methylenebiscyclohexyl diisocyanate, 2,2′-methylenebiscyclohexyl diisocyanate and mixtures thereof; IPDI such as isophorone diisocyanate; Hydrogenated XDI such as cyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane and mixtures thereof; 1,3-cyclopentene diisocyanate, 1,4-cyclohexanedi Alicyclic diisocyanates such as socyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate; HDI such as hexamethylene diisocyanate; trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene Aliphatic diisocyanates such as diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate Can be mentioned. These may be used alone or in combination of two or more. In addition, when an aliphatic or alicyclic type is used, since it becomes the composition for adhesive agents which is hard to color, it is preferable.

  Further examples of the polyisocyanate (c) include the isocyanate multimer (dimer, trimer, pentamer, heptamer, etc.), urethane-modified product, biuret-modified product, allophanate-modified product, and urea-modified product. Is mentioned. Furthermore, a blocked isocyanate in which a blocking agent such as ε-caprolactam, methyl ethyl ketone oxime, a pyrazole compound, or a malonic acid diester is bonded to an isocyanate group can also be used. Usually, one type of polyisocyanate is selected and used, but two or more types may be selected and used from these polyisocyanates.

  The amount of polyisocyanate (c) used is the equivalent ratio (NCO / OH) of isocyanate groups (NCO) derived from polyisocyanate to hydroxyl groups (OH) derived from polyester polyol (a) and polycarbonate diol (b). It is preferable that it is 1.5-10. If the value of NCO / OH is 1.5 or more, the adhesive force of the adhesive composition does not decrease over time, and if it is 10 or less, the adhesive composition having sufficient adhesive force is obtained. can get. The value of NCO / OH is further preferably 2 to 8, and more preferably 2 to 5.

[Other ingredients]
The composition for adhesives of this embodiment can also contain a chain extender as needed. Although it does not specifically limit as chain extender, Specifically, Short chain diols, such as ethylene glycol and 1, 4- butanediol; Ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diphenyl Diamines such as diamine, diaminodiphenylmethane, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine; and water, but are not limited thereto. Normally, one type of chain extender is selected and used, but two or more types may be selected from these chain extenders and used in combination. It is preferable that the usage-amount of a chain extender is 1-50 mol% with respect to the sum total of polyester polyol (a) and polycarbonate diol (b).

  The usage object of the composition for adhesives of this embodiment is not specifically limited, For example, it can use for a plastics, a metal, wood, glass, etc. When using this glass composition for adhesives as a base material, such as a glass surface, metal foil, a metal plate, or a metal vapor deposition film, a silane coupling agent can be contained in order to improve adhesive strength. Although it does not specifically limit as a silane coupling agent, Specifically, Vinyl silanes, such as vinyl tris ((beta) -methoxyethoxy) silane, vinyl ethoxysilane, vinyl trimethoxysilane; (gamma)-(meth) acryloxypropyl trimethoxysilane (Meth) acryloxysilanes such as γ- (meth) acryloxypropyldimethoxymethylsilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxy Silane, β- (3,3-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxy Epoxy such as silane Orchids; N-β- (aminoethyl) -γ-aminopropylmethoxysilane, N-β- (aminoethyl) -γ-aminopropylethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxy Examples include aminosilanes such as silane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane. These silane coupling agents may be used alone or in combination of two or more. The addition amount of a silane coupling agent may be 0.1-10 mass% normally with respect to the sum total of polyester polyol (a) and polycarbonate diol (b).

  A reaction accelerator can be used for the composition for adhesives of this embodiment as needed. Although it does not specifically limit as a reaction accelerator, Specifically, Organometallic compounds, such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dimaleate; Nitrogen-containing compounds, such as triethylamine, triethylenediamine, and morpholine; Potassium acetate, stearic acid Examples thereof include metal salts such as zinc and tin octylate. Usually, you may add the quantity of 0.00001-0.1 mass% with respect to the sum total of polyester polyol (a), polycarbonate diol (b), and polyisocyanate (c).

  Additives such as a flame retardant, an ultraviolet absorber, an antioxidant, a leveling agent, and an antifoaming agent may be used in the adhesive composition of the present embodiment as necessary.

  The flame retardant is not particularly limited, and specific examples include antimony trioxide and brominated polystyrene.

  Although it does not specifically limit as a ultraviolet absorber, Specifically, a benzotriazole type, a triazine type, a salicylic acid derivative type, and a benzophenone type are mentioned.

  Although it does not specifically limit as antioxidant, Specifically, hindered phenol type | system | groups, such as 1,1,3-tri (4-hydroxy-2-methyl-5-t-butylphenyl) butane, 4,4 Examples include thioethers such as' -thiobis [2-t-butyl-5-methylphenol] bis [3- (dodecylthio) propionate].

  The leveling agent is not particularly limited, but specifically, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified hydroxyl group-containing polydimethylsiloxane, acrylic copolymer Products, methacrylic copolymers, polyether-modified polymethylalkylsiloxanes, acrylic acid alkyl ester copolymers, and methacrylic acid alkyl ester copolymers.

  The antifoaming agent is not particularly limited, and specifically, silicone oil such as high molecular weight polydimethylsiloxane, modified silicone oil such as amino group-introduced silicone oil, nonionic surfactant such as polyoxyethylene alkyl ether, mineral Oil.

  The composition for adhesives of this embodiment can contain 10-100 mass% of inert organic solvents as needed. Examples of the inert organic solvent include, but are not limited to, solvents such as pentane, hexane, cyclohexane, methylcyclohexane, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, and xylene. It is done. These inert organic solvents are used alone or in admixture of two or more.

The application amount of the adhesive composition of the present embodiment may usually be 0.5 to 10 g / m ² as a solid content. When the coating amount is 0.5 g / m ² or more, sufficient adhesive strength is obtained and the possibility of poor appearance is small. A coating amount of 10 g / m ² or less is preferable because the adhesive does not leak from the end of the film.

  The composition for adhesives of this embodiment may be used as a two-pack type adhesive for mixing polyester polyol (a) and polycarbonate diol (b) with polyisocyanate (c) at the time of use. It can also be used as a one-component adhesive in which polyol (a), polycarbonate diol (b), and polyisocyanate (c) are premixed.

[Method for producing composition for adhesive]
The manufacturing method of the composition for adhesives is not specifically limited, It can manufacture with the mixing method generally used, An organic solvent and a catalyst can be used as needed. For example, a polyester polyol (a) and a polycarbonate diol (b) are added to an organic solvent, and the mixture is stirred to obtain a uniform solution. The polyisocyanate (c) and a catalyst are added to the solution, and the mixture is stirred. Can be prepared.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited at all by these examples.
The physical property values shown in the following examples and comparative examples were measured by the following methods.

1) Primary terminal OH ratio of polycarbonate diol The primary terminal OH ratio of polycarbonate diol was measured by the following method. Weigh about 70 to 100 g of polycarbonate diol in a 300 cc eggplant flask and heat at about 180 ° C. while stirring under a pressure of 0.1 kPa or less using a rotary evaporator connected to a trap bulb for collecting fractions. The polycarbonate diol was heated in a bath to obtain an initial fraction corresponding to 1 to 2% by mass of the polycarbonate diol in the trap sphere, that is, about 1 g (0.7 to 2 g) of an initial fraction. This was recovered using about 100 g (95 to 105 g) of ethanol as a solvent, and the peak value of the chromatogram obtained by subjecting the recovered solution to GC analysis was calculated by the following formula (1).
Primary terminal OH ratio (%) = A ÷ B × 100 (1)
A: Sum of peak areas of diols whose both ends are primary OH groups B: Sum of peak areas of alcohols (excluding ethanol) containing diol Gas chromatographic analysis conditions: Column; DB-WAX (US & J Company) Manufactured), 30 m, film thickness 0.25 μm, temperature rising condition: 60 ° C. to 250 ° C., detector: FID (flame ionization detector)

2) Number average molecular weight of polycarbonate diol The hydroxyl value is determined by “neutralization titration method (JIS K 0070-1992)” in which acetic anhydride and pyridine are used and titrated with an ethanol solution of potassium hydroxide. Used to calculate the number average molecular weight.
Number average molecular weight = 2 / (OH value × 10 ⁻³ /56.1) (2)

3) Copolymerization ratio and main component ratio of polycarbonate diol 1 g of a sample was taken into a 100 ml eggplant flask, 30 g of ethanol and 4 g of potassium hydroxide were added, and reacted at 100 ° C. for 1 hour. After cooling the reaction solution to room temperature, 2-3 drops of phenolphthalein was added to the indicator and neutralized with hydrochloric acid. After cooling in the refrigerator for 1 hour, the precipitated salt was removed by filtration and analyzed using GC (gas chromatography). GC analysis was performed using gas chromatography GC-14B (manufactured by Shimadzu Corporation, Japan) with DB-WAX (manufactured by J & W, USA) as a column, diethylene glycol diethyl ester as an internal standard, and FID as a detector. The temperature rising profile of the column was maintained at 60 ° C. for 5 minutes and then heated to 250 ° C. at 10 ° C./min.

(I) Copolymerization ratio Using the above analysis results, from the molar ratio of 1,5-pentanediol and 1,6-hexanediol, the copolymerization ratio (1,5-pentanediol with 100 as a whole) Number of moles: number of moles of 1,6-hexanediol).
(Ii) Main component ratio It calculated | required by following Numerical formula (3) using said analysis result.
Main component ratio (mol%) = {(B + C) / A} × 100 (3)
A: Total number of moles of diol derived from the repeating unit of the above formula (A)
B: Number of moles of 1,5-pentanediol
C: Number of moles of 1,6-hexanediol

4) Purity analysis of polycarbonate diol raw material diol 1,5-hexanediol and 1,6-hexanediol used as diol raw materials were analyzed by gas chromatography. The conditions were gas chromatography GC-14B (manufactured by Shimadzu Corporation) with DB-WAX (manufactured by J & W) as a column, diethylene glycol diethyl ester as an internal standard, and FID as a detector. The temperature rising profile of the column was maintained at 60 ° C. for 5 minutes and then heated to 250 ° C. at 10 ° C./min.

5) Production of laminate film Using solvent-free laminator on polyester film (manufactured by Toray Industries, Inc., Lumirror X-10S, thickness 50 μm), for adhesives so that the solid content weight is ² to 2.5 g / m ² . After apply | coating a composition and volatilizing a solvent, it was bonded together with the polyester film (Toray Co., Ltd. product, Lumirror X-10S, thickness 50 micrometers). After aging at 40 ° C. for 3 days, it was used for the following evaluation.

6) Evaluation of appearance After the aging was completed, the sample was further allowed to stand at 40 ° C. for 1 week, and then the test piece was visually observed.
Evaluation criteria ◎: No abnormality ○: Slightly turbid or uneven △: Slightly turbid ×: Turbid or bleed

7) Measurement of adhesive strength Measured according to JIS K6854-3 (adhesive-peel adhesion strength test method-Part 3: T-shaped peel). Evaluation was made with an average value (unit: N / 25 mm) of five test pieces.

8) Durability evaluation of adhesive strength Predetermined time (2000 hours) elapses with 60 minutes of one cycle, 12 minutes of precipitation repeated in a sunshine type weatherometer (Suga Test Instruments, WEL-SUN-DC) Processed until. Thereafter, the adhesive strength was measured by the same method as described in “Measurement of initial adhesive strength” in 7) above.

[Polymerization example 1 of polycarbonate diol (b)]
1,5-pentanediol and 1,6-hexanediol used as raw materials were analyzed. The 1,5-pentanediol had a purity of 98.4% and contained 1.2% by mass of 1,5-hexanediol and 0.1% by mass of 1,4-cyclohexanediol. The remaining 0.3% by mass was a plurality of unknown items. The 1,6-hexanediol had a purity of 98.9% and contained 0.7% by mass of 1,4-cyclohexanediol. The remaining 0.4 mass% was a plurality of unknown items. In the following polymerization examples, the raw materials were used except for polymerization examples 6 and 13 of the polycarbonate diol (b).

  In a 2 L glass flask equipped with a rectification column packed with a regular packing and a stirring device, 650 g (7.4 mol) of ethylene carbonate, 370 g (3.6 mol) of 1,5-pentanediol, 450 g (3.8 mol) of hexanediol was charged. As a catalyst, 0.20 g of titanium tetrabutoxide was added and stirred and heated at normal pressure. The reaction temperature was 150 ° C. to 190 ° C., and the pressure was 3.0 to 5.0 kPa, and the reaction was performed for 10 hours while distilling off the mixture of ethylene glycol and ethylene carbonate to be produced. Thereafter, the pressure was reduced to 0.5 kPa, and the mixture was further reacted at 190 ° C. for 5 hours while distilling off ethylene carbonate and diol. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC1.

[Polymerization example 2 of polycarbonate diol (b)]
The reaction was carried out with the apparatus shown in Polymerization Example 1 for polycarbonate diol (b) in the amount of raw materials charged. As a catalyst, 0.20 g of titanium tetrabutoxide was added and stirred and heated at normal pressure. The reaction temperature was 150 ° C. to 190 ° C., and the pressure was 3.0 to 5.0 kPa, and the reaction was performed for 10 hours while distilling off the mixture of ethylene glycol and ethylene carbonate to be produced. Thereafter, the pressure was reduced to 0.5 kPa, and the mixture was further reacted at 190 ° C. for 3 hours while distilling off ethylene carbonate and diol. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC2.

[Polymerization example 3 of polycarbonate diol (b)]
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol (b), 700 g (7.8 mol) of dimethyl carbonate, 450 g (4.3 mol) of 1,5-pentanediol, and 450 g (3. 8 mol) was charged. Titanium tetrabutoxide 0.20 g was added as a catalyst, heated and stirred at a temperature of 140 to 150 ° C. under normal pressure, and reacted for 8 hours while distilling off the resulting mixture of methanol and dimethyl carbonate. Thereafter, the reaction temperature was set to 150 ° C. to 190 ° C., and the reaction was performed for 2 hours at a pressure of 10 to 15 kPa while distilling off the mixture of methanol and dimethyl carbonate produced. Then, it was made to react at 190 degreeC for 5 hours, reducing pressure gradually to 0.5kPa. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC3.

[Polymerization example 4 of polycarbonate diol (b)]
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol (b), 700 g (7.8 mol) of dimethyl carbonate, 480 g (4.6 mol) of 1,5-pentanediol, and 400 g (3. 4 mol) was charged. Titanium tetrabutoxide 0.20 g was added as a catalyst, heated and stirred at a temperature of 140 to 150 ° C. under normal pressure, and reacted for 8 hours while distilling off the resulting mixture of methanol and dimethyl carbonate. Thereafter, the reaction temperature was set to 150 ° C. to 190 ° C., and the reaction was performed for 2 hours at a pressure of 10 to 15 kPa while distilling off the mixture of methanol and dimethyl carbonate produced. Then, it was made to react at 190 degreeC for 5 hours, reducing pressure gradually to 0.5kPa. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC4.

[Polymerization example 5 of polycarbonate diol (b)]
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol (b), 730 g (6.2 mol) of diethyl carbonate, 250 g (2.4 mol) of 1,5-pentanediol, and 500 g (4. 2 mol) was charged. Titanium tetrabutoxide 0.20 g was added as a catalyst, heated and stirred at a temperature of 140 to 150 ° C. under normal pressure, and reacted for 8 hours while distilling off the resulting mixture of ethanol and diethyl carbonate. Thereafter, the reaction temperature was 150 ° C. to 190 ° C., and the reaction was performed for 2 hours at a pressure of 10 to 15 kPa while distilling off the resulting mixture of ethanol and diethyl carbonate. Then, it was made to react at 190 degreeC for 5 hours, reducing pressure gradually to 0.5kPa. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC5.

[Polymerization example 6 of polycarbonate diol (b)]
Raw materials 1,5-pentanediol and 1,6-hexanediol were purified by distillation. As a result, 1,5-pentanediol had a purity of 99.0%, contained 0.4% by mass of 1,5-hexanediol, and 1,4-cyclohexanediol was not detected. The remaining 0.6 mass% was a plurality of unknown items. The 1,6-hexanediol had a purity of 99.1% and contained 0.3% by mass of 1,4-cyclohexanediol. The remaining 0.6 mass% was a plurality of unknown items. Polycarbonate diol was polymerized using the above raw materials.

  Using the same apparatus as in Polymerization Example 1 for polycarbonate diol (b), 810 g (6.9 mol) of diethyl carbonate, 370 g (3.6 mol) of 1,5-pentanediol, and 450 g (3. 8 mol) was charged. Titanium tetrabutoxide 0.20 g was added as a catalyst, heated and stirred at a temperature of 140 to 150 ° C. under normal pressure, and reacted for 8 hours while distilling off the resulting mixture of ethanol and diethyl carbonate. Thereafter, the reaction temperature was 150 ° C. to 190 ° C., and the reaction was performed for 2 hours at a pressure of 10 to 15 kPa while distilling off the resulting mixture of ethanol and diethyl carbonate. Then, it was made to react at 190 degreeC for 5 hours, reducing pressure gradually to 0.5kPa. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC6.

[Polymerization example 7 of polycarbonate diol (b)]
The reaction was carried out with the apparatus shown in Polymerization Example 1 for polycarbonate diol (b) in the amount of raw materials charged. As a catalyst, 0.20 g of titanium tetrabutoxide was added and stirred and heated at normal pressure. The reaction temperature was 150 ° C. to 190 ° C., and the pressure was 3.0 to 5.0 kPa, and the reaction was performed for 8 hours while distilling off the mixture of ethylene glycol and ethylene carbonate to be produced. Thereafter, the pressure was reduced to 0.5 kPa, and the mixture was further reacted at 190 ° C. for 2 hours while distilling off ethylene carbonate and diol. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC7.

[Polymerization example 8 of polycarbonate diol (b)]
Reaction was performed by the method shown in Polymerization Example 1 for polycarbonate diol (b), and the reaction was further continued at 190 ° C. for 8 hours. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC8.

[Polymerization example 9 of polycarbonate diol (b)]
Reaction was performed by the method shown in Polymerization Example 8 of polycarbonate diol (b), and the reaction was further continued at 190 ° C. for 12 hours. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC9.

[Polymerization example 10 of polycarbonate diol (b)]
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol (b), 770 g (6.5 mol) of diethyl carbonate, 460 g (4.4 mol) of 1,5-pentanediol, and 300 g (2. 5 mol) was charged. Titanium tetrabutoxide 0.20 g was added as a catalyst, heated and stirred at a temperature of 140 to 150 ° C. under normal pressure, and reacted for 8 hours while distilling off the resulting mixture of ethanol and diethyl carbonate. Thereafter, the reaction temperature was 150 ° C. to 190 ° C., and the reaction was performed for 2 hours at a pressure of 10 to 15 kPa while distilling off the resulting mixture of ethanol and diethyl carbonate. Then, it was made to react at 190 degreeC for 5 hours, reducing pressure gradually to 0.5kPa. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC10.

[Polymerized diol polymerization example 11]
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol (b), 580 g (6.4 mol) of dimethyl carbonate and 800 g (6.8 mol) of 1,6-hexanediol were charged. Titanium tetrabutoxide 0.20 g was added as a catalyst, heated and stirred at a temperature of 140 to 150 ° C. under normal pressure, and reacted for 8 hours while distilling off the resulting mixture of methanol and dimethyl carbonate. Thereafter, the reaction temperature was set to 150 ° C. to 190 ° C., and the reaction was performed for 2 hours at a pressure of 10 to 15 kPa while distilling off the mixture of methanol and dimethyl carbonate produced. Then, it was made to react at 190 degreeC for 5 hours, reducing pressure gradually to 0.5kPa. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC11.

[Polymerized diol polymerization example 12]
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol (b), 750 g (8.3 mol) of dimethyl carbonate, 480 g (4.6 mol) of 1,5-pentanediol, and 400 g (3. 4 mol) was charged. Titanium tetrabutoxide 0.20 g was added as a catalyst, heated and stirred at a temperature of 140 to 150 ° C. under normal pressure, and reacted for 6 hours while distilling off the resulting mixture of methanol and dimethyl carbonate. Thereafter, the reaction temperature was 150 ° C. to 210 ° C., and the reaction was performed at a pressure of 9 to 15 kPa for 2 hours while distilling off the mixture of methanol and dimethyl carbonate produced. Then, it was made to react at 210 degreeC for 3 hours, reducing pressure gradually to 0.5kPa. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC12.

[Polymerized diol polymerization example 13]
1,5-pentanediol and 1,6-hexanediol used in Polymerization Example 6 of polycarbonate diol (b) were used. In the apparatus shown in Polymerization Example 1 for polycarbonate diol (b), 630 g (7.2 mol) of ethylene carbonate, 350 g (3.4 mol) of 1,5-pentanediol, and 450 g (3.8 mol) of 1,6-hexanediol were used. ) Prepared. As a catalyst, 0.20 g of titanium tetrabutoxide was added and stirred and heated at normal pressure. The reaction temperature was 150 ° C. to 190 ° C., and the pressure was 3.0 to 5.0 kPa, and the reaction was performed for 10 hours while distilling off the mixture of ethylene glycol and ethylene carbonate to be produced. Thereafter, the pressure was reduced to 0.5 kPa, and the mixture was further reacted at 190 ° C. for 5 hours while distilling off ethylene carbonate and diol. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC13.

[Polymerized diol polymerization example 14]
In the apparatus shown in Polymerization Example 1 for polycarbonate diol (b), 660 g (7.5 mol) of ethylene carbonate, 160 g (1.5 mol) of 1,5-pentanediol, and 90 g (0.8 mol) of 1,6-hexanediol were used. ), 470 g (5.2 mol) of 1,4-butanediol was charged. As a catalyst, 0.20 g of titanium tetrabutoxide was added and stirred and heated at normal pressure. The reaction temperature was 150 ° C. to 190 ° C., and the pressure was 3.0 to 5.0 kPa, and the reaction was performed for 10 hours while distilling off the mixture of ethylene glycol and ethylene carbonate to be produced. Thereafter, the pressure was reduced to 0.5 kPa, and the mixture was further reacted at 190 ° C. for 5 hours while distilling off ethylene carbonate and diol. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC14.

[Polymerized diol polymerization example 15]
In the polymerization example 11 of polycarbonate diol, the same apparatus was used and the reaction was performed under the same conditions except that 1,6-hexanediol was changed to 710 g (6.8 mol) of 1,5-pentanediol. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC15.

[Polymerized diol polymerization example 16]
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol (b), 780 g (6.6 mol) of diethyl carbonate, 210 g (2.0 mol) of 1,5-pentanediol, and 600 g of 1,6-hexanediol (5. 1 mol) was charged. Titanium tetrabutoxide 0.20 g was added as a catalyst, heated and stirred at a temperature of 140 to 150 ° C. under normal pressure, and reacted for 8 hours while distilling off the resulting mixture of ethanol and diethyl carbonate. Thereafter, the reaction temperature was 150 ° C. to 190 ° C., and the reaction was performed for 2 hours at a pressure of 10 to 15 kPa while distilling off the resulting mixture of ethanol and diethyl carbonate. Then, it was made to react at 190 degreeC for 5 hours, reducing pressure gradually to 0.5kPa. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC16.

[Polymerized diol polymerization example 17]
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol (b), 740 g (6.3 mol) of diethyl carbonate, 500 g (4.8 mol) of 1,5-pentanediol, and 230 g of 1,6-hexanediol (2. 0 mol) was charged. Titanium tetrabutoxide 0.20 g was added as a catalyst, heated and stirred at a temperature of 140 to 150 ° C. under normal pressure, and reacted for 8 hours while distilling off the resulting mixture of ethanol and diethyl carbonate. Thereafter, the reaction temperature was 150 ° C. to 190 ° C., and the reaction was performed for 2 hours at a pressure of 10 to 15 kPa while distilling off the resulting mixture of ethanol and diethyl carbonate. Then, it was made to react at 190 degreeC for 5 hours, reducing pressure gradually to 0.5kPa. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC17.

[Polymer polyol (a) polymerization example]
Into a 2 L reactor equipped with a stirrer, 570 g (3.4 mol) of isophthalic acid, 370 g (2.5 mol) of adipic acid, 210 g (3.4 mol) of ethylene glycol, 190 g (1.8 mol) of neopentylfricol 1, 160 g (1.4 mol) of 6-hexanediol was charged and reacted at 200 to 230 ° C. for 6 hours under a nitrogen stream. After adding 0.1 g of tetraisobutyltitanium, the pressure was gradually reduced. The reaction was further performed at a pressure of 1.2 to 2.5 hPa and a temperature of 230 to 250 ° C. for 6 hours. The number average molecular weight of the obtained polyester polyol was 12000, and the hydroxyl value was 9.4. In the following examples and comparative examples, this polyester polyol was used. The hydroxyl value was determined by a “neutralization titration method (JIS K 0070-1992)” in which acetic anhydride and pyridine were used and titrated with an ethanol solution of potassium hydroxide.

[Example 1]
To 160 ml of ethyl acetate, 100 g of polyester polyol (a) and 25 g of PC1 as polycarbonate diol (b) were added and stirred to obtain a uniform solution. Thereto, 43 g of isocyanurate structure type TPA-100 (manufactured by Asahi Kasei Chemicals Corporation, NCO content 23.1%) as polyisocyanate (c) and 0.017 g of dioctyltin dilaurate as a catalyst were added and stirred. An adhesive composition was prepared.

  A laminate film was prepared using the obtained adhesive composition, and the appearance, initial adhesive strength (measured with a test piece immediately after aging under predetermined conditions), and durability of adhesive strength were evaluated. The evaluation results are shown in Table 2.

[Example 2]
To 135 ml of ethyl acetate, 100 g of polyester polyol (a) and 25 g of PC2 as polycarbonate diol (b) were added and stirred to obtain a uniform solution. Thereto, 64 g of isocyanurate structure type TPA-100 (manufactured by Asahi Kasei Chemicals Corporation, NCO content 23.1%) as polyisocyanate (c), and 0.019 g of dioctyltin dilaurate as a catalyst were added and stirred. An adhesive composition was prepared.

  A laminate film was prepared using the obtained adhesive composition, and the appearance, initial adhesive strength (measured with a test piece immediately after aging under predetermined conditions), and durability of adhesive strength were evaluated. The evaluation results are shown in Table 2.

[Examples 3-6, Example 10, Comparative Examples 1-7]
An adhesive composition was prepared by the method shown in Example 1 except that PC3-6 and 10-17 were used as the polycarbonate diol.

  A laminate film was prepared using the obtained adhesive composition, and the appearance, initial adhesive strength (measured with a test piece immediately after aging under predetermined conditions), and durability of adhesive strength were evaluated. The evaluation results are shown in Table 2.

[Example 7]
To 160 ml of ethyl acetate, 80 g of polyester polyol (a) and 25 g of PC7 as polycarbonate diol (b) were added and stirred to obtain a uniform solution. Thereto, 100 g of isocyanurate structure type TPA-100 (manufactured by Asahi Kasei Chemicals Corporation, NCO content 23.1%) as polyisocyanate (c), 0.023 g of dioctyltin dilaurate as a catalyst, and stirred, An adhesive composition was prepared.

  A laminate film was prepared using the obtained adhesive composition, and the appearance, initial adhesive strength (measured with a test piece immediately after the laminate film was prepared and aged under predetermined conditions), and durability of the adhesive strength were evaluated. The evaluation results are shown in Table 2.

[Example 8]
100 g of polyester polyol (a) and 25 g of PC8 as polycarbonate diol (b) were added to 110 ml of ethyl acetate and stirred to obtain a uniform solution. Thereto, 23 g of isocyanurate structure type TPA-100 (manufactured by Asahi Kasei Chemicals Corporation, NCO content 23.1%) as polyisocyanate (c) and 0.015 g of dioctyltin dilaurate as a catalyst were added and stirred. An adhesive composition was prepared.

  A laminate film was prepared using the obtained adhesive composition, and the appearance, initial adhesive strength (measured with a test piece immediately after the laminate film was prepared and aged under predetermined conditions), and durability of the adhesive strength were evaluated. The evaluation results are shown in Table 2.

[Example 9]
100 g of polyester polyol (a) and 25 g of PC9 as a polycarbonate diol were added to 100 ml of ethyl acetate and stirred to obtain a uniform solution. Due to the high viscosity of the solution, an additional 100 ml of ethyl acetate was added. Thereto, 17 g of isocyanurate structure type TPA-100 (manufactured by Asahi Kasei Chemicals Corporation, NCO content 23.1%) was added as a polyisocyanate (c) and stirred to prepare an adhesive composition. A laminate film was prepared using the obtained adhesive composition, and the appearance, initial adhesive strength (measured with a test piece immediately after the laminate film was prepared and aged under predetermined conditions), and durability of the adhesive strength were evaluated. The evaluation results are shown in Table 2.

  From the results shown in Table 2, it is found that the adhesive composition according to the present invention has a good appearance after aging at a high temperature, and is excellent in initial adhesive strength and durability of adhesive strength. It was.

  ADVANTAGE OF THE INVENTION According to this invention, the composition for adhesive agents which has tough adhesive force, can maintain adhesive force over a long period of time, and the external appearance after hardening is favorable is obtained. Therefore, this adhesive composition can be used for bonding various substrates such as plastic, metal, wood, and glass. In particular, since this adhesive composition has flexibility and transparency, it can be suitably used as an adhesive for a solar cell back surface sealing sheet.

Claims (2)

Containing polyester polyol (a), polycarbonate diol (b), and polyisocyanate (c);
The polycarbonate diol (b) is a polycarbonate diol having a repeating unit represented by the following formula (A) and a terminal hydroxyl group,
60 to 100 mol% of the repeating unit represented by the following formula (A) is a repeating unit represented by the following formula (B) and the following formula (C),
The ratio of the repeating unit represented by the following formula (B) and the repeating unit represented by the following formula (C) is 70:30 to 30:70 (molar ratio),
The primary terminal OH ratio is 95 to 99.5%.
Adhesive composition.
(In the formula, R represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 15 carbon atoms.)
  The composition for adhesives of Claim 1 whose number average molecular weights of the said polycarbonate diol (b) are 450-1250.