CN107835845B - Adhesive composition and surface protective film - Google Patents
Adhesive composition and surface protective film Download PDFInfo
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- CN107835845B CN107835845B CN201680041066.2A CN201680041066A CN107835845B CN 107835845 B CN107835845 B CN 107835845B CN 201680041066 A CN201680041066 A CN 201680041066A CN 107835845 B CN107835845 B CN 107835845B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
Abstract
The present invention addresses the problem of providing an adhesive composition that can provide an adhesive film having excellent resistance to whitening under wet heat and humidity environments and excellent contamination resistance to an adherend. The present invention provides an adhesive composition characterized by containing a polyurethane (A) having 2 or more hydroxyl groups, a crosslinking agent (B), a carbodiimide compound (C), and an organic solvent (D). The present invention also provides a surface protective film having a cured coating film of the adhesive composition. The adhesive composition of the present invention can be particularly suitably used as an adhesive layer of a surface protective film. The adhesive composition of the present invention can provide an adhesive film having excellent whitening resistance under a moist heat resistant environment and excellent stain resistance to an adherend.
Description
Technical Field
The present invention relates to an adhesive composition that can be suitably used as a surface protective film.
Background
Surface protection films are widely used for the purpose of preventing dirt and scratches on the surfaces of glass, plastic, and the like.
As the structure of the surface protective film, for example, a surface protective film in which a plastic film such as a polyethylene terephthalate film, an adhesive layer, and a release film are laminated is used (for example, see patent document 1). As the adhesive used for the adhesive layer, a silicone adhesive, an acrylic adhesive, a urethane adhesive, and the like are widely used.
In particular, in the manufacturing process of a touch panel peripheral member used in a smartphone or a tablet personal computer, the use of a protective film using a polyurethane adhesive is increasing from the viewpoints of efficiency of a bonding operation and price advantage. However, in the case of using a polyurethane-based protective film, there are the following problems: in a moist heat resistant environment such as during the production process, during the subsequent transportation process, or during use, the adherend is contaminated or whitening occurs due to moist heat.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2013-124293
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing an adhesive composition that can provide an adhesive film having excellent resistance to whitening under wet heat and humidity environments and excellent contamination resistance to an adherend.
Means for solving the problems
The present invention provides an adhesive composition characterized by containing: a polyurethane (A) having 2 or more hydroxyl groups, a crosslinking agent (B), a carbodiimide compound (C), and an organic solvent (D).
The present invention also provides a surface protective film having a cured coating film of the adhesive composition.
Effects of the invention
The adhesive composition of the present invention can provide an adhesive film having excellent whitening resistance under a moist heat resistant environment and excellent stain resistance to an adherend. In addition, when a specific ester compound is further contained in the pressure-sensitive adhesive composition, in addition to the above effects, wettability to an adherend and stain resistance to an adherend under a moist heat resistant environment can be further improved. Therefore, the adhesive composition of the present invention can be particularly suitably used as an adhesive layer of a surface protective film.
Detailed Description
The adhesive composition of the present invention contains a polyurethane (a) having 2 or more hydroxyl groups, a crosslinking agent (B), a carbodiimide compound (C), and an organic solvent (D) as essential components.
The polyurethane (a) has 2 or more hydroxyl groups for crosslinking with the crosslinking agent (B) described later, and preferably has 4 to 8 hydroxyl groups. The polyurethane (a) is crosslinked with the crosslinking agent (B), whereby excellent adhesive properties, stain resistance and whitening resistance can be obtained.
As the polyurethane (a), for example, a polyurethane obtained by reacting a polyol (a' 1) with a polyisocyanate (a2) can be used.
As the polyol (a' 1), for example, polyoxyalkylene polyol (a1), polyester polyol, polycarbonate polyol, polybutadiene polyol, polycaprolactone polyol, acryl polyol, dimer diol, polyisoprene polyol, and the like can be used. These polyols may be used alone, or 2 or more kinds may be used in combination. Among these, from the viewpoint of further improving the flexibility of the adhesive and the stain resistance and whitening resistance derived from the hydrolysis property of polyurethane, the polyoxyalkylene polyol (a1) is preferably used.
As the polyoxyalkylene polyol (a1), for example, polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol, polyoxyethylene polyoxypropylene polyol, polyoxyethylene polyoxybutylene polyol, polyoxypropylene polyoxybutylene polyol and the like can be used. These polyoxyalkylene polyols may be used alone, or 2 or more kinds may be used in combination. In addition, as the polyoxyalkylene polyol, from the viewpoint of reactivity with the polyisocyanate (a2), a polyoxyalkylene polyol having 2 to 6 hydroxyl groups is preferably used, and more preferably having 2 to 4 hydroxyl groups.
The content of the oxyalkylene structure in the polyurethane (a) is preferably in the range of 5 to 30mol/kg, more preferably in the range of 10 to 20mol/kg, and further preferably in the range of 13 to 17mol/kg, from the viewpoint of obtaining more excellent stain resistance and whitening resistance by improving the hydrophilicity of the polyurethane.
The polyoxyalkylene polyol (a1) preferably contains a polyoxypropylene glycol and/or a polyoxyethylene polyoxypropylene triol, and more preferably contains a polyoxypropylene glycol and a polyoxyethylene polyoxypropylene triol, from the viewpoint of imparting flexibility to a pressure-sensitive adhesive and obtaining further excellent wettability to an adherend.
Further, the molar ratio [ EO/PO ] of the oxyethylene structure to the oxypropylene structure in the polyoxyalkylene polyol (a1) is preferably in the range of 5/95 to 60/40, more preferably in the range of 10/90 to 30/70, from the viewpoint that the stain resistance and whitening resistance can be further improved by improving the hydrophilicity of the polyurethane.
The number average molecular weight of the polyol (a' 1) containing the polyoxyalkylene polyol (a1) is preferably in the range of 500 to 6,000, more preferably 800 to 3,000, from the viewpoint of good adhesive properties and mechanical strength of the adhesive film. The number average molecular weight of the polyol (a' 1) is a value measured by a Gel Permeation Chromatography (GPC) method under the following conditions.
A measuring device: high-speed GPC apparatus (HLC-8220 GPC, manufactured by Tosoh corporation)
Column: the following columns manufactured by Tosoh corporation were connected in series for use.
"TSKgel G5000" (7.8 mmI.D.. times.30 cm). times.1 roots
"TSKgel G4000" (7.8mm I.D.. times.30 cm). times.1 roots
"TSKgel G3000" (7.8 mmI.D.. times.30 cm). times.1 roots
"TSKgel G2000" (7.8 mmI.D.. times.30 cm). times.1 roots
A detector: RI (differential refractometer)
Column temperature: 40 deg.C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100 μ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: the calibration curve was made using the following standard polystyrene.
(Standard polystyrene)
TSKgel Standard polystyrene A-500 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-1000 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-2500 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-5000 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-1 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-2 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-4 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-10 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-20 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-40 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-80 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-128 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-288 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-550 manufactured by Tosoh corporation "
Further, the polyol (a' 1) may be used in combination with a chain extender having a number average molecular weight of 50 to 400, if necessary.
Examples of the chain extender include ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 3-methyl-1, 5-pentanediol, 2-butyl-2-ethylpropanediol, neopentyl glycol, 1, 4-cyclohexanediol, and 1, 4-cyclohexanedimethanol. These chain extenders may be used alone, or 2 or more of them may be used in combination.
Examples of the polyisocyanate (a2) include aromatic polyisocyanates such as xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate. These polyisocyanates may be used alone, or 2 or more kinds may be used in combination. Among these, aliphatic or alicyclic polyisocyanates are preferably used from the viewpoint of maintaining good adhesion and further suppressing the secondary discoloration.
As a method for producing the polyurethane (a), for example, a method in which the polyisocyanate (a2) and the polyol (a' 1) are reacted so that the molar ratio of the hydroxyl groups in the two is excessive relative to the molar ratio of the isocyanate groups in the polyisocyanate is mentioned. The reaction may be carried out in an organic solvent (D) described later. The polyol (a' 1) may be fed all at once, or may be fed in 2 or more times while controlling the reaction. The molar ratio (NCO/OH) of the hydroxyl group of the polyol (a' 1) to the isocyanate group of the polyisocyanate (a2) is preferably in the range of 0.3 to 0.99, more preferably in the range of 0.4 to 0.9, from the viewpoints of easiness of reactivity control and mechanical strength of the adhesive film.
The weight average molecular weight of the polyurethane (a) is preferably in the range of 50,000 to 300,000, and more preferably in the range of 70,000 to 200,000, from the viewpoint of satisfying both adhesive properties and wettability to an adherend at a high level. The weight average molecular weight of the polyurethane (a) is a value measured in the same manner as the number average molecular weight of the polyol (a' 1).
As the crosslinking agent (B), for example, a polyisocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, and the like can be used. These crosslinking agents may be used alone, or 2 or more kinds may be used in combination. Among these, an isocyanate crosslinking agent is preferably used from the viewpoint of obtaining good adhesive properties, stain resistance and whitening resistance by reacting with the hydroxyl group of the polyurethane (a) and increasing the crosslinking density of the adhesive.
As the polyisocyanate crosslinking agent, polyisocyanates such as toluene diisocyanate, chlorobenzene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and xylylene diisocyanate; trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, trimethylolpropane adduct of xylylene diisocyanate, isocyanurate body of hexamethylene diisocyanate (ヌレ - ト body), isocyanurate body of tolylene diisocyanate, isocyanurate body of isophorone diisocyanate, isocyanurate body of xylylene diisocyanate, and the like. These crosslinking agents may be used alone, or 2 or more kinds may be used in combination.
The amount of the crosslinking agent (B) used is preferably in the range of 0.01 to 20 parts by mass, and more preferably in the range of 0.1 to 15 parts by mass, based on 100 parts by mass of the polyurethane (a), from the viewpoint of obtaining good adhesive properties, stain resistance and whitening resistance.
The carbodiimide compound (C) is an essential component for exhibiting excellent whitening resistance and excellent wettability and stain resistance to various adherends regardless of the substrate and the adherend. The reason why the above-mentioned effects are obtained by using the carbodiimide compound (C) is to prevent the transfer of the decomposed product derived from the base material to the adherend, which is generated under high humidity and heat.
Examples of the carbodiimide compound (C) include N, N '-dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, N- [3- (dimethylamino) propyl ] -N '-ethylcarbodiimide, and N- [3- (dimethylamino) propyl ] -N' -ethylcarbodiimide methiodide, carbodiimide compounds such as N-t-butyl-N '-ethylcarbodiimide, N-cyclohexyl-N' - (2-morpholinoethyl) carbodiimide meso-p-toluenesulfonic acid, N '-di-t-butylcarbodiimide, and N, N' -di-p-tolylcarbodiimide; polycarbodiimide obtained by subjecting a polyisocyanate to a known condensation reaction in the presence of a carbodiimidization catalyst, and the like. These carbodiimide compounds may be used alone, or 2 or more kinds may be used in combination. Among these, carbodiimide compounds having an isocyanate group are preferably used because they react with hydroxyl groups of the polyurethane (a) to provide more excellent stain resistance and whitening resistance.
Examples of the carbodiimide compound (C) include "Carbodilite V-02", "Carbodilite V-02-L2", "Carbodilite V-04", "Carbodilite V-05", "Carbodilite V-07", "Carbodilite V-09", "Carbodilite E-01", "Carbodilite E-02", "Carbodilite E-03A" and Carbodilite E-04 "(available from Nisshinbo Chemicals Co., Ltd., above) which are commercially available.
The amount of the carbodiimide compound (C) used is preferably in the range of 0.1 to 7 parts by mass, more preferably in the range of 0.5 to 5 parts by mass, based on 100 parts by mass of the polyurethane (a-1), from the viewpoint of obtaining excellent whitening resistance, wettability to an adherend, and stain resistance.
The organic solvent (D) is used for improving the production stability of the polyurethane (A-1) and the coatability of the adhesive composition, and for example, ester solvents such as ethyl acetate, methyl acetate, butyl acetate and the like; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as heptane, hexane, cyclohexane, methylcyclohexane and the like; aromatic hydrocarbon solvents such as toluene, o-xylene, m-xylene, and p-xylene; and alcohol solvents such as methanol, ethanol, isopropanol, isobutanol, sec-butanol, and tert-butanol. These organic solvents may be used alone, or 2 or more of them may be used in combination.
The amount of the organic solvent (D) is preferably 20 to 200 parts by mass, and more preferably 40 to 100 parts by mass, based on 100 parts by mass of the polyurethane (a), from the viewpoint of coatability.
The pressure-sensitive adhesive composition of the present invention contains the polyurethane (a), the crosslinking agent (B), the carbodiimide compound (C), and the organic solvent (D) as essential components, but preferably further contains an ester compound (E) obtained by esterifying at least 1 or more hydroxyl groups of a polyoxyethylene glycol with a monobasic acid, from the viewpoints of further improving wettability to an adherend, suppressing a large increase in adhesive strength even in a moist heat resistant environment, and further improving stain resistance to an adherend.
The reason why the above-mentioned effects are obtained by using the ester (E) is that further flexibility and hydrophilicity can be imparted to the adhesive.
The number average molecular weight of the polyoxyethylene glycol is preferably in the range of 100 to 1,500, and more preferably in the range of 150 to 1,000, from the viewpoint of obtaining good wettability to an adherend by softening of the adhesive and improving stain resistance by bleeding of the adhesive. The number average molecular weight of the polyoxyethylene glycol is a value measured in the same manner as the number average molecular weight of the polyol (a' 1).
Examples of the monobasic acid include saturated fatty acids such as butyric acid, valeric acid, caproic acid, enanthic acid, 2-ethylhexanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid; unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, eicosenoic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, ricinoleic acid, and the like. Among these, from the viewpoint of obtaining good compatibility with polyurethane, a saturated fatty acid having 6 to 18 carbon atoms and/or an unsaturated fatty acid having 14 to 18 carbon atoms is preferably used, and 1 or more types of monobasic acids selected from 2-ethylhexanoic acid, lauric acid, and oleic acid are more preferably used.
The amount of the ester (E) used is preferably in the range of 1 to 50 parts by mass, more preferably in the range of 5 to 30 parts by mass, per 100 parts by mass of the polyurethane (a), from the viewpoint of obtaining excellent wettability to an adherend and stain resistance to an adherend under a moist heat resistant environment.
The pressure-sensitive adhesive composition of the present invention contains the above-mentioned components (A) to (D) as essential components, more preferably contains the above-mentioned component (E), and may further contain other additives as required.
As the other additives, for example, an antioxidant, a plasticizer, a rust preventive, a thixotropic agent, a dispersant, a sensitizer, a urethane catalyst, a polymerization inhibitor, a leveling agent, a thickener, a foam stabilizer, and the like can be used. These additives may be used alone, or 2 or more of them may be used in combination.
The method for producing the pressure-sensitive adhesive composition of the present invention includes, for example, a method in which the polyurethane (a) is dissolved in the organic solvent (D), and the crosslinking agent (B), the carbodiimide compound (C), and the ester compound (E) are added to and mixed with the resulting mixture.
As described above, the pressure-sensitive adhesive composition of the present invention can provide a pressure-sensitive adhesive film having excellent whitening resistance under a moist heat resistant environment and excellent stain resistance to an adherend. In addition, when the pressure-sensitive adhesive composition further contains a specific ester compound, in addition to the above effects, wettability to an adherend and stain resistance to an adherend under a moist heat resistant environment can be further improved. Therefore, the adhesive composition of the present invention can be particularly suitably used as an adhesive layer of a surface protective film.
Examples of a method for producing a surface protective film using the adhesive composition include a method in which the adhesive composition is applied to a plastic substrate, dried and cured to obtain an adhesive layer, and then a release film is attached to the adhesive layer.
Examples of the plastic substrate include sheets and films made of polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, polyolefins, polyacrylates, polyvinyl chloride, polyethylene, polypropylene ethylene vinyl alcohol, polyurethane, polyamide and polyimide. The surface of these plastic substrates may be subjected to a mold release treatment, an antistatic treatment, a corona treatment, or the like. The thickness of the plastic base material is, for example, in the range of 10 to 200. mu.m.
Examples of the method for applying the adhesive composition to the plastic substrate include coating methods using a roll coater, a gravure coater, a reverse coater, a spray coater, an air knife coater, a die coater, and the like.
The thickness of the coated adhesive layer after drying with the organic solvent (D) is, for example, in the range of 5 to 100 μm.
After the adhesive composition is applied to the plastic substrate, the adhesive composition is dried, for example, at 50 to 120 ℃ for 30 seconds to 10 minutes. After drying, aging may be performed, for example, in the range of 30 to 50 ℃ from the viewpoint of accelerating the curing reaction.
Examples
The present invention will be described in more detail below with reference to examples.
[ Synthesis example 1]
< Synthesis of polyurethane (A-1) >
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 330 parts by mass of polyester Polyol (Kuraray co., ltd. "Kuraray Polyol P1010", number average molecular weight: 1,000, hereinafter abbreviated as "P1010"), 150 parts by mass of hexamethylene diisocyanate (hereinafter abbreviated as "HDI"), 0.01 part by mass of dioctyltin dilaurate, and 430 parts by mass of ethyl acetate were placed in a separable flask, and heated to 70 ℃. After confirming that the isocyanate group content reached the content calculated from the amount of the charged compound by titration with dibutylamine and hydrochloric acid, the mixture was cooled to 40 ℃. Subsequently, 960 parts by mass of polyoxyethylene polyoxypropylene triol (SUNNIX GL-3000 manufactured by Sanyo chemical Co., Ltd., number average molecular weight; 3,000, molar ratio [ EO/PO ] ═ 25/75, hereinafter abbreviated as "GL-3000"), 0.02 part by mass of dioctyltin dilaurate, and 345 parts by mass of ethyl acetate were put in a separable flask and reacted at 70 ℃ for 3 hours to obtain nonvolatile components: 65 mass%, viscosity: 10,000mPa · s, weight average molecular weight: 130,000, content of polyoxyalkylene: 12mol/kg of polyurethane (A-1).
[ Synthesis example 2]
< Synthesis of polyurethane (A-2) >
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, and a thermometer, 330 parts by mass of polyoxypropylene glycol (number average molecular weight: 1,000, hereinafter abbreviated as "PPG 1000"), 150 parts by mass of HDI, 0.2 parts by mass of dioctyltin dilaurate, and 430 parts by mass of ethyl acetate were placed in a separable flask, and heated to 70 ℃. After confirming that the isocyanate group content reached the content calculated from the amount of the charged compound by titration with dibutylamine and hydrochloric acid, the mixture was cooled to 40 ℃. Subsequently, GL-3000960 parts by mass and ethyl acetate 345 parts by mass were charged into a separable flask, and reacted at 70 ℃ for 3 hours, thereby obtaining nonvolatile components: 65 mass%, viscosity: 15,500mPa · s, weight average molecular weight: 130,000, content of polyoxyalkylene: 16mol/kg of polyurethane (A-2).
[ Synthesis example 3]
< Synthesis of polyurethane (A-3) >
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 1,800 parts by mass of polyoxyethylene polyoxypropylene triol (manufactured by Nichikoku corporation, "unicave 50 TG-32", number average molecular weight: 2,800, molar ratio [ EO/PO ] (57/43, hereinafter abbreviated as "50 TG-32")/HDI 150 parts by mass, dioctyltin dilaurate 0.2 parts by mass, and ethyl acetate 830 parts by mass were placed in a separable flask, heated to 70 ℃ and reacted to obtain nonvolatile components: 75 mass%, viscosity: 2,000mPa · s, weight average molecular weight: 70,000, content of polyoxyalkylene: 18mol/kg of polyurethane (A-3).
[ example 1]
An adhesive composition was obtained by mixing 1 part by mass of a carbodiimide compound "Carbodilite V-05" (hereinafter, abbreviated as "V-05") produced by Nisshinbo Co., Ltd and 10 parts by mass of an isocyanurate compound of hexamethylene diisocyanate (hereinafter, abbreviated as "TKA-100" produced by Asahi Kasei corporation) as a crosslinking agent with respect to 100 parts by mass of the nonvolatile component of the polyurethane (A-1) obtained in Synthesis example 1.
Next, the pressure-sensitive adhesive composition was applied to the surface of a polyethylene terephthalate film having a thickness of 50 μm so that the dried film thickness became 10 μm, and dried at 80 ℃ for 3 minutes. A polyethylene terephthalate film having a thickness of 38 μm and subjected to a mold release treatment was bonded to the surface of the film, and the film was cured at 40 ℃ for 3 days to obtain a surface protective film.
[ examples 2 to 10]
An adhesive composition and a surface protective film were obtained in the same manner as in example 1, except that the kinds and/or amounts of the polyurethane (a), the crosslinking agent (B), and the carbodiimide compound (C) used were changed as shown in table 1.
Comparative example 1
A pressure-sensitive adhesive composition and a surface protective film were obtained in the same manner as in example 1, except that the carbodiimide compound (C) was not used.
[ comparative examples 2 to 4]
An adhesive composition and a surface protective film were obtained in the same manner as in comparative example 1, except that the kinds and/or amounts of the polyurethane (a) and the crosslinking agent (B) used were changed as shown in table 2.
[ method for measuring adhesive force ]
The surface protective films obtained in examples and comparative examples were cut into surface protective films having a width of 20mm to prepare test pieces. The release film was peeled from the test piece, and the glass plate was adhered by reciprocating 2 times with a 2kg roller so that the adhesion area became 20mm × 60 mm. After 24 hours of pasting, the adhesive tape was peeled at 180 degrees under an atmosphere of 23 ℃ and a humidity of 50% to obtain an initial adhesive force (N/25 mm). After the above-mentioned pasting, the adhesive sheet was left to stand at 85 ℃ and 85% humidity for 72 hours and then left to stand at 23 ℃ for 24 hours, and then was subjected to 180-degree peel strength to obtain a wet heat resistant adhesive strength (N/25 mm).
[ evaluation method of whitening resistance ]
The release films of the surface protective films obtained in examples and comparative examples were peeled off and attached to a glass plate. The haze (%) of the test piece was measured by a haze meter "NDH 5000" (manufactured by Nippon Denshoku industries Co., Ltd.) according to JIS K7361-1-1997. Subsequently, the test piece thus obtained was left to stand at 85 ℃ and 85% RH for 100 hours (hereinafter, referred to as "after wet heat resistance test") and then taken out at 23 ℃ and 50% RH. After the removal, the haze (%) was measured by a haze meter "NDH 5000" (manufactured by Nippon Denshoku industries Co., Ltd.) in accordance with JIS K7361-1-1997 within 10 minutes, and the whitening resistance was evaluated in the following manner.
". o": the difference in haze (%) between before and after the wet heat resistance test was less than 0.3%.
"Δ": the difference in haze (%) between before and after the wet heat resistance test is 0.3% or more and less than 1%.
"×": the difference in haze (%) between before and after the wet heat resistance test was 1% or more.
[ method for evaluating stain resistance ]
The release films of the surface protective films obtained in examples and comparative examples were peeled off and attached to a glass plate. At this time, air bubbles were introduced between the adhesive film and the glass plate. The test piece was left at 85 ℃ and 85% humidity for 72 hours. After the sheet was left to stand at 23 ℃ for 24 hours, the adhesive film was peeled off from the glass plate by hand, and the LED lamp was irradiated from the lower part of the glass plate to visually observe the state of contamination and evaluate the film as described below.
"O"; the glass sheets were completely free of contamination.
"Δ"; contamination was confirmed only in a part of the glass plate.
"×"; contamination was confirmed over the entire surface of the glass plate.
[ Table 1]
[ Table 2]
Abbreviations in tables 1 to 2 are described.
"V-07"; carbodilite V-07, a carbodiimide Compound manufactured by Nisshinbo Co., Ltd "
"V-09"; carbodiimide Compound "Carbodilite V-09" manufactured by Nisshinbo Co., Ltd "
"P301-75E"; trimethylolpropane adduct of hexamethylene diisocyanate (Duranate P301-75E, manufactured by Asahi Kasei Chemicals Co., Ltd.)
[ example 11]
To the pressure-sensitive adhesive composition obtained in example 1, 10 parts by mass of an esterified product (E-1) obtained by esterifying both ends of polyoxyethylene glycol (number-average molecular weight; 200) with 2-ethylhexanoic acid was further added as an esterified product (E), to obtain a pressure-sensitive adhesive composition.
Next, the pressure-sensitive adhesive composition was applied to the surface of a polyethylene terephthalate film having a thickness of 50 μm so that the dried film thickness became 10 μm, and dried at 80 ℃ for 3 minutes. A polyethylene terephthalate film having a thickness of 38 μm and subjected to a mold release treatment was bonded to the surface of the film, and the film was cured at 40 ℃ for 3 days to obtain a surface protective film.
[ examples 12 to 18]
An adhesive composition and a surface protective film were obtained in the same manner as in example 1, except that the kinds and/or amounts of the polyurethane (a), the crosslinking agent (B), the carbodiimide compound (C) and the ester (E) used were changed as shown in table 3.
Comparative example 6
A pressure-sensitive adhesive composition and a surface protective film were obtained in the same manner as in example 1, except that the carbodiimide compound (C) was not used.
[ comparative examples 5 to 8]
An adhesive composition and a surface protective film were obtained in the same manner as in comparative example 5, except that the kinds and/or amounts of the polyurethane (a) and the crosslinking agent (B) used were changed as shown in table 4.
[ method for evaluating wettability ]
The surface protective films obtained in examples and comparative examples were cut into a rectangular shape having a width of 5cm and a length of 15cm, and the release film was peeled off, and the surface protective films obtained thereby were used as test pieces. The test piece was bent by holding both ends of the test piece with hands, the center of the exposed adhesive layer was adhered to the glass plate, and then the hands were released, and the number of seconds until the adhesive film was adhered to the glass plate by its own weight was measured.
[ Table 3]
[ Table 4]
Abbreviations in tables 3 to 4 are described.
"E-2": esterified product of polyoxyethylene glycol (number average molecular weight: 600) having both ends esterified with 2-ethylhexanoic acid
"E-3"; an esterified product of a polyoxyethylene glycol (number average molecular weight: 500) having one end esterified with lauric acid
Therefore, the following steps are carried out: the adhesive composition of the present invention is excellent in whitening resistance and stain resistance to an adherend even under a moist heat resistant environment. In addition, it is known that: examples 9 to 16 containing the ester (E) were excellent in wettability to an adherend and were able to suppress an increase in adhesive strength after a wet heat resistance test.
On the other hand, comparative examples 1 to 8 are embodiments in which the carbodiimide compound (C) was not used, and all of them were confirmed to be contaminated with an adherend.
Claims (6)
1. An adhesive composition comprising: a polyurethane (A) having 2 or more hydroxyl groups, a crosslinking agent (B), a carbodiimide compound (C) and an organic solvent (D),
the amount of the crosslinking agent (B) used is in the range of 0.01 to 20 parts by mass per 100 parts by mass of the polyurethane (A),
the amount of the carbodiimide compound (C) used is in the range of 0.1 to 7 parts by mass per 100 parts by mass of the polyurethane (A),
the polyurethane (A) has a structure derived from a polyoxyalkylene polyol (a1) and a polyisocyanate (a2),
the polyoxyalkylene polyol (a1) contains a polyoxypropylene glycol and a polyoxyethylene polyoxypropylene triol, and the molar ratio of the oxyethylene structure to the oxypropylene structure in the polyoxyalkylene polyol (a1) is 5/95 to 60/40 as EO/PO.
2. The adhesive composition according to claim 1, wherein the content of the oxyalkylene structure in the polyurethane (A) is in the range of 5 to 30 mol/kg.
3. The adhesive composition of claim 1, wherein the crosslinker (B) is a polyisocyanate crosslinker.
4. The adhesive composition according to claim 1, further comprising an esterified product (E) in which at least 1 or more hydroxyl groups of the polyoxyethylene glycol are esterified with a monobasic acid.
5. The adhesive composition according to claim 4, wherein the amount of the ester (E) used is in the range of 1 to 50 parts by mass per 100 parts by mass of the polyurethane (A).
6. A surface protective film having a cured coating film of the adhesive composition according to any one of claims 1 to 5.
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| JP2015141365 | 2015-07-15 | ||
| JP2015-141365 | 2015-07-15 | ||
| PCT/JP2016/064144 WO2017010158A1 (en) | 2015-07-15 | 2016-05-12 | Pressure-sensitive adhesive composition and surface protection film |
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| WO2020026935A1 (en) * | 2018-08-01 | 2020-02-06 | Dic株式会社 | Adhesive composition and surface protection film |
| JP7388814B2 (en) * | 2018-10-29 | 2023-11-29 | リンテック株式会社 | Shatterproof adhesive sheet |
| CN112996875B (en) * | 2018-11-06 | 2023-05-26 | Dic株式会社 | Adhesive composition and surface protective film |
| JP6863538B2 (en) * | 2018-11-29 | 2021-04-21 | Dic株式会社 | Adhesive composition and surface protective film |
| CN109796921B (en) * | 2019-01-30 | 2021-03-26 | 广东盈通新材料有限公司 | Modified polyurethane adhesive, composite waterproof strip comprising modified polyurethane adhesive, and preparation method and application of composite waterproof strip |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103068873A (en) * | 2010-08-06 | 2013-04-24 | Dic株式会社 | Urethane resin composition, coating agent, urethane resin composition for producing surface layer of leather-like sheet, laminate and leather-like sheet |
| US8906976B2 (en) * | 2011-11-01 | 2014-12-09 | Hyundai Motor Company | Polyurethane compositions for an automotive seat |
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| JP2003155321A (en) * | 2001-09-10 | 2003-05-27 | Toyo Ink Mfg Co Ltd | Urethane resin composition |
| JP2003292928A (en) * | 2002-02-04 | 2003-10-15 | Toyo Ink Mfg Co Ltd | Urethane resin adhesive and laminate |
| JP2006182795A (en) * | 2004-12-24 | 2006-07-13 | Mitsubishi Chemicals Corp | Polyurethane pressure-sensitive adhesive composition, and pressure-sensitive adhesive sheet and surface-protecting film |
| JP5137319B2 (en) * | 2006-04-11 | 2013-02-06 | 日東電工株式会社 | Adhesive composition, adhesive sheet and surface protective film |
| JP5456440B2 (en) * | 2009-01-30 | 2014-03-26 | 日東電工株式会社 | Dicing tape integrated wafer back surface protection film |
| CN102648094B (en) * | 2009-12-04 | 2015-04-08 | 东洋纺织株式会社 | Highly adhesive thermoplastic resin film |
| JP2014162821A (en) * | 2013-02-22 | 2014-09-08 | Nitto Denko Corp | Surface protection film |
| JP6092034B2 (en) * | 2013-07-30 | 2017-03-08 | 日東電工株式会社 | Surface protective film and optical member |
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| CN103068873A (en) * | 2010-08-06 | 2013-04-24 | Dic株式会社 | Urethane resin composition, coating agent, urethane resin composition for producing surface layer of leather-like sheet, laminate and leather-like sheet |
| US8906976B2 (en) * | 2011-11-01 | 2014-12-09 | Hyundai Motor Company | Polyurethane compositions for an automotive seat |
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| TW201708483A (en) | 2017-03-01 |
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