CN111748311A - Ultraviolet-curable adhesive composition for protective film, cured product, and protective plate - Google Patents

Ultraviolet-curable adhesive composition for protective film, cured product, and protective plate Download PDF

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Publication number
CN111748311A
CN111748311A CN202010222479.9A CN202010222479A CN111748311A CN 111748311 A CN111748311 A CN 111748311A CN 202010222479 A CN202010222479 A CN 202010222479A CN 111748311 A CN111748311 A CN 111748311A
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meth
acrylate
adhesive composition
ultraviolet
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CN111748311B (en
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增原义洋
罗聪
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Arakawa Chemical Industries Ltd
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Arakawa Chemical Industries Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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    • G02B1/14—Protective coatings, e.g. hard coatings
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    • C09J2475/00—Presence of polyurethane

Abstract

The present invention provides an ultraviolet-curable adhesive composition for a protective film, which provides a cured product having low adhesion force and excellent self-adsorption property during curing and having little generation of chips, a cured product, and a protective plate. [ solution ] an ultraviolet-curable adhesive composition for protective films, which comprises: a specific polyurethane (a) which is a reactant of a polyol (a1), a polyisocyanate (a2), a hydroxyl group-containing (meth) acrylate (a3), and a hydroxyl group-containing photopolymerization initiator (a 4); an alkyl mono (meth) acrylate (B) having an alkyl group with 6 to 18 carbon atoms; a polyfunctional (meth) acrylate (C); a plasticizer (D), and the component (A) satisfies specific conditions.

Description

Ultraviolet-curable adhesive composition for protective film, cured product, and protective plate
Technical Field
The present invention relates to an ultraviolet-curable adhesive composition for a protective film, a cured product, and a protective plate.
Background
In a manufacturing process of an optical component or the like, a protective film is temporarily attached to a surface of the component in order to suppress generation of damage, dirt, or the like in each process during processing, transportation, inspection, or the like. The protective film is usually eventually peeled off and discarded. In recent years, demand for protective films has increased, and protective films more suitable for protecting optical components have been particularly desired.
As a protective film for an optical member, it is required that even when the protective film is peeled off due to some problem in the process, the protective film can be bonded to the member again in a manner of being attached to the member, and the surface of the optical member is not damaged; further, it is necessary to be easily peelable to prevent the optical member and the liquid crystal cell from being misaligned or having an enlarged cell gap due to deformation caused by peeling. The optical component to which the protective film is attached is cut into an appropriate shape by a cutter or the like according to the application. If chips are generated during this cutting, the chips may adhere to the member, and dirt, cracks, and the like may be generated. Therefore, it is important for an ultraviolet-curable adhesive composition for attaching a protective film to reduce the generation of chips in addition to self-adhesiveness and low adhesive force at the time of curing.
As a pressure-sensitive adhesive focusing on low adhesion and removability, for example, a removable pressure-sensitive adhesive composition composed of an ethylenically unsaturated group-containing hydrophilic acrylic polymer, a photopolymerization initiator, and a crosslinking agent is known (patent document 1). However, the adhesive composition becomes low adhesive force after ultraviolet irradiation, but does not become low adhesive force after thermal curing. Further, since a large amount of solvent is contained, a step of removing the solvent is required in producing the adhesive sheet.
On the other hand, as a solvent-free type ultraviolet curable adhesive, for example, an ultraviolet curable adhesive composition composed of a urethane (meth) acrylate having a polyethylene glycol skeleton, a (meth) acrylic monomer, and a photopolymerization initiator is known (patent document 2). However, this adhesive composition cannot be peeled off because the layer composed of the cured product has high adhesive force, and is likely to generate chips.
Documents of the prior art
Patent document
[ patent document 1] Japanese patent application laid-open No. 2001-019911
[ patent document 2] Japanese patent No. 5641382
Disclosure of Invention
Technical problem to be solved by the invention
The invention provides an ultraviolet curing adhesive composition for a protective film, a cured product and a protective plate, wherein the ultraviolet curing adhesive composition provides a cured product which has low adhesive force and excellent self-adsorption property and generates less cutting scraps during curing.
Means for solving the problems
The present inventors have made intensive studies focusing on the composition of an adhesive composition, and have found that the above-mentioned technical problems are solved by appropriately combining a specific polyurethane, a plurality of (meth) acrylates, and a plasticizer, and have completed the present invention. Namely, the present invention relates to the following ultraviolet-curable pressure-sensitive adhesive composition for a protective film, a cured product, and a protective plate.
1. An ultraviolet-curable adhesive composition for a protective film, comprising:
a polyurethane (a) which is a reactant of a polyol (a1), a polyisocyanate (a2), a hydroxyl group-containing (meth) acrylate (a3), and a hydroxyl group-containing photopolymerization initiator (a 4);
an alkyl mono (meth) acrylate (B) having an alkyl group with 6 to 18 carbon atoms;
a polyfunctional (meth) acrylate (C);
a plasticizer (D) which is a mixture of a plasticizer,
in the component (a), the introduction rate of the skeleton derived from the component (a3) and the introduction rate of the skeleton derived from the component (a4) are 5 to 95 mol% with respect to the blocked isocyanate groups of the urethane prepolymer composed of the component (a1) and the component (a2), respectively.
2. The ultraviolet-curable adhesive composition for protective films as described in the above item 1, wherein the component (a1) is a polyether polyol and/or a polyester polyol.
3. The ultraviolet-curable pressure-sensitive adhesive composition for protective films as described in the above item 1 or 2, wherein the component (a3) is a hydroxyl group-containing mono (meth) acrylate and/or a hydroxyl group-containing di (meth) acrylate.
4. The ultraviolet-curable pressure-sensitive adhesive composition for protective films as described in any one of the above items 1 to 3, wherein the total of the component (A), the component (B) and the component (C) is 100% by mass, the component (A) is 20 to 84% by mass, the component (B) is 15 to 79% by mass, and the component (C) is 1 to 65% by mass.
5. The ultraviolet-curable adhesive composition for protective films as described in any one of the above items 1 to 4, wherein the component (D) comprises at least 1 selected from the group consisting of saturated fatty acid esters, nonreactive ester polymers, acrylic polymers and rosins containing no conjugated bonds.
6. The ultraviolet-curable pressure-sensitive adhesive composition for protective films as described in any one of the above items 1 to 5, wherein the component (D) is 1 to 50% by mass based on 100% by mass of the total of the components (A), (B) and (C).
7. A cured product of the ultraviolet-curable pressure-sensitive adhesive composition for protective films as described in any one of the above items 1 to 6.
8. A protective plate having a layer comprising the cured product according to the above item 7 on at least one surface of a member.
Advantageous effects
According to the ultraviolet-curable adhesive composition for protective films (hereinafter also simply referred to as "adhesive composition") of the present invention, a layer composed of a cured product of the adhesive composition (hereinafter referred to as "cured layer") has low adhesive force and is therefore easily peeled from a member at the time of peeling; further, the adhesive tape was quickly attached to a member at the time of attachment ( dyed む) (hereinafter referred to as "self-adhesive property"). In addition, the generation of chips during cutting is also small (hereinafter referred to as "cuttability").
Drawings
FIG. 1 is a graph showing the case where the evaluation result of the cuttability is ". smallcircle".
FIG. 2 is a graph showing a case where the evaluation result of the cuttability is "Delta".
FIG. 3 is a graph showing the results of evaluation of cuttability "X".
Detailed Description
The adhesive composition of the present invention contains a specific polyurethane (A) (hereinafter referred to as component (A)), an alkyl mono (meth) acrylate (B) (hereinafter referred to as component (B)) having an alkyl group with 6 to 18 carbon atoms, a polyfunctional (meth) acrylate (C) (hereinafter referred to as component (C)), and a plasticizer (D) (hereinafter referred to as component (D)).
(A) Component (a) is a reaction product of a polyol (a1) (hereinafter referred to as component (a 1)), a polyisocyanate (a2) (hereinafter referred to as component (a 2)), a hydroxyl group-containing (meth) acrylate (a3) (hereinafter referred to as component (a 3)), and a hydroxyl group-containing photopolymerization initiator (a4) (hereinafter referred to as component (a 4)).
(a1) The component (b) is an alcohol having 2 or more hydroxyl groups, and contributes to the self-adsorption property of the pressure-sensitive adhesive composition of the present invention. As the component (a1), either a single compound polyol or a polymer polyol may be used, or either a crystalline polyol or an amorphous polyol may be used. Herein, the crystalline polyol means a polyol having a crystal structure preferably at 20 to 60 ℃, more preferably at 20 to 40 ℃.
The polyhydric alcohol as the single compound is not particularly limited, and examples thereof include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 2-diethyl-1, 3-propanediol, 1, 9-nonanediol, 1, 10-decanediol, butylethylpropanediol, and butylethylpentanediol; alicyclic diols such as 1, 4-cyclohexanedimethanol; trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, dimer diol (ダイマージオール), hydrogenated dimer diol, trimer triol (トリマートリオール), hydrogenated trimer triol, castor oil-type modified polyols, and alkylene oxide adducts of bisphenol compounds or derivatives thereof. These may be used alone, or 2 or more of them may be used in combination.
The polymer polyol is not particularly limited, and examples thereof include polyether polyol, polyester polyol, poly (meth) acrylic polyol, polyolefin polyol, polycaprolactone polyol, polycarbonate polyol, and the like. These may be used alone, or 2 or more of them may be used in combination. In addition, (meth) acrylic acid ((メタ) アクリル) means acrylic acid or methacrylic acid.
Among these, polymer polyols are preferable from the viewpoint of self-adsorption of the cured product layer. Specific polymer polyols are shown below by way of example.
The polyether polyol is not particularly limited, and examples thereof include: in addition to polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, copolymers containing a plurality of alkylene oxides (alkylene oxide-other alkylene oxide) as monomer components, such as ethylene oxide-propylene oxide copolymers, and the like. These may be used alone, or 2 or more of them may be used in combination.
Commercially available polyether polyols include "ADEKA polyether P-400", "ADEKA polyether G-400", "ADEKA polyether T-400", "ADEKA polyether AM-302", "ADEKA polyether P1000" and "ADEKA polyether P2000" (manufactured by ADEKA, Co., Ltd.); "polyethylene glycol #1,540" (manufactured by Nacalai Tesque (ナカライテスク) (strain)); dipropylene glycol and polypropylene glycol 400 (manufactured by pure chemical Co., Ltd.); PTMG650, PTMG1000, PTMG2000 and PTMG3000 (manufactured by Mitsubishi ケミカル Co., Ltd.).
The polyester polyol is not particularly limited, and examples thereof include polycondensates of polyols and polycarboxylic acids; ring-opening polymers of cyclic esters (lactones); and reactants of a polyol, a polycarboxylic acid, and a cyclic ester.
The polyol is not particularly limited, and examples thereof include the polyols listed above as single-compound polyols; trihydric alcohols such as glycerin, trimethylolpropane and trimethylolethane; cyclohexanediols such as 1, 2-cyclohexanediol, 1, 3-cyclohexanediol and 1, 4-cyclohexanediol; cyclohexanedimethanol such as 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol and 1, 4-cyclohexanedimethanol; bisphenols such as bisphenol a and bisphenol F; xylitol, sorbitol and other sugar alcohols, these can be used alone, can also be combined with 2 or more.
The polycarboxylic acid is not particularly limited, and examples thereof include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as 1, 4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, and trimellitic acid (トリメリット acid), and these may be used alone or in combination of 2 or more.
The cyclic ester is not particularly limited, and examples thereof include propiolactone, β -methyl-valerolactone, and caprolactone, and these may be used alone or in combination of 2 or more.
Commercially available polyester polyols include "PolyLite RX-4800(ポリライト RX-4800)", "PolyLite OD-X-2523", "PolyLite OD-X-2547", "PolyLite OD-X-2420", "PolyLite OD-X-2692" and "PolyLite OD-X-2108" (manufactured by DIC Co., Ltd.); "Kuraray polyol P-510" and "Kuraray polyol F-510" (manufactured by Kuraray (クラレ) Co., Ltd.) were used.
Examples of the polycarbonate polyol include a reaction product of a polyol and phosgene; ring-opening polymers of cyclic carbonates (alkylene carbonates, etc.), and the like. The polyol includes the above-mentioned polyol. The alkylene carbonate is not particularly limited, and examples thereof include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. As a commercial product of the polycarbonate polyol, "Kuraray polyol C-590" ((manufactured by Kuraray Co., Ltd.); "NIPPOLLAN 4002", "NIPPOLLAN 4009", "NIPPOLLAN 981" (manufactured by DOW ソ -); "DURANOL T6002" and "DURANOL T5652" (manufactured by Asahi Kasei Corp., Ltd.).
Examples of the poly (meth) acrylic polyol include homopolymers and copolymers of acrylic monomers having 1 or more hydroxyl groups, and copolymers obtained by copolymerizing these copolymers with other monomers, and these may be used alone or in combination of 2 or more.
As a commercially available product of a poly (meth) acrylic polyol, "ARUFON UH-2041" (manufactured by Toyo Seiya Kabushiki Kaisha); "acrylic polyol # 6000" (manufactured by Taisii Fine Chemical, Inc. フ ァ イ ン ケミカル); "acrylic polyol PC # 5984" (manufactured by Toronghua Kabushiki Kaisha), and the like.
The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene having 2 or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorides thereof. These may be used alone, or 2 or more of them may be used in combination. Examples of commercially available products include "NISSO-PB GI-1000", "NISSO-PB GI-2000" and "NISSO-PB GI-3000" (manufactured by Nippon Caoda Co., Ltd.).
The polycaprolactone polyol is not particularly limited, and examples thereof include polycaprolactone diol, polycaprolactone triol, and polycaprolactone tetraol, and these can be used alone or in combination of 2 or more. Examples of commercially available products include "PolyLite OD-X-2155" (manufactured by DIC Co., Ltd.); "PLACCEL 200", "PLACCEL 205", "PLACCEL 300", "PLACCEL 400" (manufactured by Daicel (ダイセル) Co., Ltd.), and the like.
Among these polymer polyols, polyether polyols and/or polyester polyols are preferred from the viewpoint of excellent self-adsorption of the cured product layer.
(a1) The physical properties of the components are not particularly limited, and for example, the number average molecular weight (polystyrene equivalent value by gel permeation chromatography) is usually about 700 to 10,000, preferably about 1,000 to 4,000, from the viewpoint of self-adsorption property of the cured product layer. In addition, from the viewpoint of low adhesive force of the cured product layer, the average number of hydroxyl groups present in 1 molecule is usually about 1.5 to 3, preferably about 2 to 3. The average number of hydroxyl groups present in 1 molecule means the average number of hydroxyl groups present in 1 molecule of the component (a 1).
The component (a2) is not particularly limited, and examples thereof include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate (キシリレンジイソシアネート); aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and the like; alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated toluene diisocyanate, and the like. These may be used alone, or 2 or more of them may be used in combination. Among these, aliphatic diisocyanates and/or alicyclic diisocyanates are preferable, particularly from the viewpoint of transparency and self-adsorptivity of the cured product layer.
(a1) The ratio of the component (a) to the component (a2) is not particularly limited, but is usually based on the number of moles of isocyanate groups of the component (a2) (NCO)(a2)) The number of moles (OH) of the hydroxyl group(s) of the component (a1)(a1)) Ratio of (NCO)(a2)/OH(a1)) Preferably, the amount is about 1.01 to 2.
The component (a3) is not particularly limited, and examples thereof include hydroxyl group-containing mono (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate; hydroxyl group-containing di (meth) acrylates such as 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, pentaerythritol di (meth) acrylate, and 2-hydroxy-1, 3-di (meth) acrylate; hydroxyl group-containing tri (meth) acrylates such as pentaerythritol tri (meth) acrylate and dipentaerythritol tri (meth) acrylate; hydroxyl group-containing tetra (meth) acrylates such as dipentaerythritol tetra (meth) acrylate; hydroxyl group-containing penta (meth) acrylates such as dipentaerythritol penta (meth) acrylate, and these may be used alone or in combination of 2 or more. Among them, from the viewpoint of self-adsorption property and low adhesion of the cured product layer, hydroxyl group-containing mono (meth) acrylate and/or hydroxyl group-containing di (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate and 2-hydroxy-3-acryloyloxypropyl (meth) acrylate are more preferable. In addition, (meth) acrylate refers to acrylate or methacrylate.
The amount of the component (a3) used is not particularly limited, but is preferably 20 to 80 mol%, more preferably 30 to 70 mol% based on 100 mol% of the blocked isocyanate groups of the urethane prepolymer composed of the component (a1) and the component (a2) from the viewpoints of self-adsorption property of the cured product layer and low adhesive force.
(a4) The component (a) is a photopolymerization initiator having at least 1 or more hydroxyl groups, and contributes to the cuttability of the cured product layer.
The component (a4) is not particularly limited, and examples thereof include 2-hydroxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl propane-1-one, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- {4- (2-hydroxy-2-methyl-propionyl) -benzyl } phenyl ] -2-methylpropan-1-one, and the like. These may be used alone, or 2 or more of them may be used in combination. Among them, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenyl propane-1-one are preferable from the viewpoint of the curability of the cured product layer.
The amount of the component (a4) used is not particularly limited, but is preferably 20 to 80 mol%, more preferably 30 to 70 mol% based on 100 mol% of the blocked isocyanate groups of the urethane prepolymer composed of the component (a1) and the component (a2) from the viewpoint of the cuttability of the cured product layer.
(A) The component (b) is not particularly limited, and can be produced by various known methods. The method is not particularly limited, and examples thereof include the following methods: after the urethane prepolymer (a1) having a blocked isocyanate group (hereinafter referred to as component (a 1)) is obtained by reacting component (a1) with component (a2), component (a1), component (A3) and component (a4) are then reacted. The component (a3) and the component (a4) may be added simultaneously or separately.
The conditions for the above reaction are not particularly limited, but the temperature is usually about 70 to 85 ℃ and the time is usually about 1 to 5 hours.
(A) The component (b) can be produced in the presence of a solvent described later, but is preferably produced in the absence of a solvent from the viewpoint of reducing environmental load. In addition, the production of the component (A) may be carried out in the presence of the component (B) described later.
By the reaction, the blocked isocyanate group derived from the component (A3) and the component (a4) is introduced by reacting these components with the blocked isocyanate group of the component (a 1).
In the component (a) of the present invention, the introduction rate of the skeleton derived from the component (a3) and the introduction rate of the skeleton derived from the component (a4) are important relative to the blocked isocyanate groups of the urethane prepolymer composed of the component (a1) and the component (a2), and affect the cuttability of the cured product layer.
The introduction rate can be calculated from the number of moles of the component (a3) and the component (a4) used in the formula (1) by partially reacting with the blocked isocyanate group of the component (a 1).
(formula 1) { introduction rate of skeleton derived from component (a3) }(%)
The number of moles used { (a3) component }/[ { (a3) component } + { (a4) component } ] × 100
The introduction rate of the skeleton derived from component (a4) can be calculated by changing the molecule of formula (1) to the number of moles used of component (a 4).
The introduction rate of the skeleton derived from the component (a3) is 5 to 95 mol%. If the introduction rate is less than 5 mol%, the (meth) acryloyl group derived from the component (a3) is small in the component (A), and thus the cured product layer cannot be sufficiently cured; if the amount exceeds 95 mol%, the amount of the skeleton derived from the component (a4) in the component (A) is small, and hence the cuttability of the cured product layer tends to deteriorate. From the same viewpoint, the amount is preferably 20 to 80 mol%, more preferably 30 to 70 mol%.
The introduction rate of the skeleton derived from the component (a4) is 5 to 95 mol%. If the introduction rate is less than 5 mol%, the skeleton derived from the component (a4) in the component (A) is small, and hence the cutting property of the cured product layer is liable to deteriorate; if the amount exceeds 95 mol%, the amount of (meth) acryloyl groups derived from the component (a3) in the component (A) is small, and therefore, it is difficult to sufficiently cure the cured product layer. From the same viewpoint, the amount is preferably 20 to 80 mol%, more preferably 30 to 70 mol%.
The molar ratio [ (a3)/(a4) ] of the component (a3) to the component (a4) relative to the blocked isocyanate groups of the urethane prepolymer composed of the component (a1) and the component (a2) is not particularly limited, but is preferably 1/4 to 4/1, and more preferably 3/7 to 7/3, from the viewpoint of curability and cuttability of the cured product layer.
The molar ratio is a ratio of the component (a3) and the component (a4) that react with the blocked isocyanate groups of the urethane prepolymer (a 1). In order to obtain the component (a) in which the component (A3) and the component (a4) are in a desired molar ratio, the component (A3) and the component (a4) in an amount to be reacted with all of them may be added to the reaction system in a desired molar ratio to the molar amount of the isocyanate groups present in the urethane prepolymer (a1) and reacted with each other.
Other physical properties of the component (a) are not particularly limited, and for example, the weight average molecular weight (polystyrene equivalent value by gel permeation chromatography) is preferably about 10,000 to 100,000, and more preferably about 10,000 to 60,000, from the viewpoint of self-adsorption property of the cured product layer.
The amount of the component (A) used is 20 to 84% by mass based on 100% by mass of the total of the components (A), (B) and (C) in terms of a solid content (the same applies hereinafter). By setting the range, the cuttability and self-adsorbability of the cured product layer become good. From the same viewpoint, the amount is preferably 25 to 75% by mass, and more preferably 30 to 70% by mass.
(B) The component (A) is alkyl mono (meth) acrylate, and the number of carbon atoms in the alkyl group is 6 to 18. When the number of carbon atoms of the alkyl group is less than 6, the low adhesion and self-adsorption properties of the cured product layer are easily deteriorated; when the number of carbon atoms of the alkyl group exceeds 18, the component (B) is highly hydrophobic, and hence the compatibility with the component (a) is liable to deteriorate.
Examples of the component (B) include n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-undecyl (meth) acrylate, n-lauryl (meth) acrylate, n-myristyl (meth) acrylate, n-cetyl (meth) acrylate, aliphatic alkyl mono (meth) acrylates such as n-stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, isoundecyl (meth) acrylate, isododecyl (meth) acrylate, isomyristyl (meth) acrylate, isopalmityl (meth) acrylate, and isostearyl (meth) acrylate; alicyclic alkyl mono (meth) acrylates such as cyclohexyl (meth) acrylate, 3, 5-trimethylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. These may be used alone, or 2 or more of them may be used in combination. Among them, from the viewpoint of self-adsorption of the cured product layer, aliphatic alkyl mono (meth) acrylates having an alkyl group with 6 to 18 carbon atoms are preferable, aliphatic alkyl mono (meth) acrylates having an alkyl group with 8 to 12 carbon atoms are more preferable, and n-lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl (meth) acrylate are further preferable.
The amount of the component (B) used is 15 to 79% by mass based on 100% by mass of the total of the components (A), (B) and (C). By setting the range, the self-adsorbability of the cured product layer becomes good. From the same viewpoint, the amount is preferably 20 to 70% by mass, and more preferably 25 to 65% by mass.
(C) The component (b) is a polyfunctional (meth) acrylate and contributes to the cuttability of the cured product layer. The component (C) is not particularly limited, and examples thereof include polyalkylene glycol poly (meth) acrylates such as hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, and the like; ester poly (meth) acrylates such as neopentyl glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate; pentaerythritol poly (meth) acrylate such as pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate; dipentaerythritol poly (meth) acrylates such as dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These can be used alone, can also be combined with 2 or more; in addition, any mixture may be used. Among these, pentaerythritol multi (meth) acrylate and dipentaerythritol multi (meth) acrylate are preferable, and dipentaerythritol multi (meth) acrylate is more preferable, from the viewpoint of satisfying both the cuttability and self-adsorbability of the cured product layer.
The amount of the component (C) used is 1 to 65% by mass based on 100% by mass of the total of the components (A), (B) and (C). By setting the range, the cured product layer can be favorably cut. From the same viewpoint, the amount is preferably 5 to 55% by mass, and more preferably 7 to 50% by mass.
(D) The component (c) is a plasticizer and contributes to self-adsorbability of the cured product layer. The component (D) is not particularly limited, but preferably does not have a carbon-carbon double bond or a carbon-carbon triple bond in the molecule from the viewpoint of satisfying both low adhesion and self-adsorption properties of the cured product layer. Examples thereof include saturated fatty acid esters such as dioctyl adipate, diisononyl adipate, dioctyl sebacate and diisononyl sebacate; aromatic carboxylates such as dimethyl phthalate, diheptyl phthalate, dioctyl phthalate, and trimellitate; phosphoric acid esters such as tributyl phosphate; non-reactive ester polymers such as polyether esters and polyesters; an acrylic polymer (obtained by polymerizing (meth) acrylic acid and/or (meth) acrylic acid ester); saturated hydrocarbon polymers such as hydrogenated polybutadiene polymers, hydrogenated polyisoprene polymers and hydrogenated polybutene polymers; rosins containing no conjugated double bond such as hydrogenated rosin, disproportionated rosin, hydrogenated rosin ester, disproportionated rosin ester and the like; hydrogenated terpene resins such as hydrogenated terpene resin and hydrogenated terpene phenol resin. These can be used alone, can also be combined with 2 or more; in addition, any of a solid state and a liquid state may be used.
Of these, from the viewpoint of increasing flexibility of the cured product layer and exhibiting excellent self-adsorption property when the adhesive composition is applied on a member, at least 1 selected from the group consisting of saturated fatty acid esters, non-reactive ester polymers, acrylic polymers and rosins containing no conjugated double bonds is preferably included, and at least 1 selected from the group consisting of dioctyl adipate, liquid acrylic polymers and disproportionated rosin esters is more preferably included.
The amount of the component (D) used is 1 to 50% by mass based on 100% by mass of the total of the components (A), (B) and (C). By setting the range, the self-adsorbability of the cured product layer becomes good. From the same viewpoint, the amount is preferably 5 to 45% by mass, and more preferably 7 to 40% by mass.
The binder composition of the present invention may further contain an α, β -unsaturated carboxylic acid such as (meth) acrylic acid or itaconic acid; styrenes such as styrene and alpha-methylstyrene; unsaturated alcohols such as α -olefin, vinyl alcohol and allyl alcohol (アリルアルコール), and salts thereof (sodium salt, potassium salt, etc.); (meth) acrylates such as hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and urethane (meth) acrylate. These may be used alone, or 2 or more of them may be used in combination. The amount of each monomer used is not particularly limited, and is usually 20% by mass or less based on 100% by mass of the adhesive composition of the present invention.
The adhesive composition of the present invention may contain various known additives as needed. The additives are not particularly limited, and examples thereof include a surface conditioner, a surfactant, an ultraviolet absorber, an antioxidant, a light stabilizer, an inorganic filler, a silane coupling agent, colloidal silica, an antifoaming agent, a wetting agent, a rust inhibitor, a crystal nucleating agent, and a crystallization accelerator. These may be used alone, or 2 or more of them may be used in combination.
The adhesive composition of the present invention can be obtained by mixing the component (a), the component (B), the component (C), and the component (D), and the above-mentioned monomers and additives as required. The mixing means and the mixing order are not particularly limited. In addition, when the component (a) is diluted with the component (B), the component (C) and the component (D) and the above-mentioned additives as needed may be mixed in a solution of the component (B) of the component (a).
The adhesive composition of the invention is substantially solvent-free, with a solvent content of less than 1 mass%, preferably less than 0.1 mass%. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, tert-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, and aromatic naphtha; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, and n-decane; alicyclic hydrocarbons such as cyclohexane; esters such as ethyl acetate, n-butyl acetate, n-pentyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, and methyl benzoate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, and methylcyclohexanone; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol.
The cured product of the present invention is obtained by curing the above adhesive composition.
The protective plate of the present invention has a layer composed of the cured product on at least one surface of a member.
The protective sheet of the present invention can be obtained by applying the adhesive composition described above to a member and then irradiating the member with ultraviolet light.
The member is not particularly limited, and examples thereof include a polyethylene terephthalate film (PET film), a cycloolefin polymer film (COP film), a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene naphthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene vinyl acetate film, an ionomer (アイオノマー) resin film, an ethylene- (meth) acrylic acid copolymer film, an ethylene- (meth) acrylate copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, and a fluororesin film. Further, a crosslinked film or a laminated film thereof may also be used. As the film, any of untreated films, films subjected to light to heavy peeling treatment, and films having an easy-adhesion layer can be used.
The coating method is not particularly limited, and examples thereof include a coater (アプリケーター), a bar coater, a roll coater, a die coater, a comma coater (コンマコーター), a knife coater, and a gravure coater.
The light source of ultraviolet rays is not particularly limited, and examples thereof include xenon lamps, high-pressure mercury lamps, and metal halide lamps. The cumulative light quantity of the ultraviolet rays and the transport speed are not particularly limited, and the cumulative light quantity is usually 100mJ/cm2～3000mJ/cm2The conveying speed is usually about 5 m/min to 50 m/min.
The thickness of the cured product layer of the present invention is not particularly limited, and is usually about 1 μm to 500 μm, preferably about 1 μm to 200 μm, from the viewpoint of low adhesion.
Examples
The present invention is specifically described below by way of examples and comparative examples. However, they do not, of course, limit the technical scope of the present invention. Unless otherwise specified, "parts" and "%" in the examples are based on mass.
(introduction ratio)
The number of moles of the component (a3) and the component (a4) used was calculated and substituted into the formula (1) and the formula (2) to obtain the introduction rate.
(introduction ratio of skeleton derived from component (a3) in component (A))
(formula 1) { introduction rate of skeleton derived from component (a3) }(%)
The number of moles used { (a3) component }/[ { (a3) component } + { (a4) component } ] × 100
(introduction ratio of skeleton derived from component (a4) in component (A))
(formula 2) { introduction rate of skeleton derived from component (a4) }(%)
The number of moles used { (a4) component }/[ { (a3) component } + { (a4) component } ] × 100
Production example 1
Into a reaction apparatus equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 561 parts of polytetramethylene glycol having a number average molecular weight of 2,000 (manufactured by mitsubishi ケミカル, ltd., trade name "PTMG 2000") (hereinafter, referred to as PTMG2000), 63 parts of hexamethylene diisocyanate (hereinafter, referred to as HDI), 217 parts of 2-ethylhexyl acrylate (hereinafter, referred to as 2-EHA), 0.4 parts of hydroquinone monomethyl ether (メトキノン) (hereinafter, referred to as MQ) and 0.1 parts of stannous octoate were charged, and after heating to 60 ℃ and heat preservation for 3 hours, a 2-EHA solution of an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Then, 133 parts of 2-EHA, 13 parts of 2-hydroxyethyl acrylate (hereinafter referred to as HEA) and 13 parts of 2-hydroxy-2-methyl-1-phenylpropanone (product name "LUNA 100" manufactured by DKSH Japan K.K.) (hereinafter referred to as LUNA100) were added thereto, and the mixture was incubated at 70 ℃ for 2 hours to measure the isocyanate value (hereinafter referred to as NCO value) and confirm completion of the reaction, thereby obtaining a 2-EHA solution of polyurethane (A-1) having a weight average molecular weight of 36,000 and an average number of acryloyl groups of 1.16. The introduction rate of the skeleton derived from the component (a3) was 58 mol%, and the introduction rate of the skeleton derived from the component (a4) was 42 mol%. The NCO value was measured in accordance with JIS K1603-1 (the same applies hereinafter).
Production example 2
576 parts of polypropylene glycol (trade name: P-2000, manufactured by ADEKA corporation) having a number average molecular weight of 2,000, 58 parts of HDI, 217 parts of 2-EHA, 0.4 part of MQ and 0.1 part of stannous octoate were charged into a reaction apparatus equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and after heating to 60 ℃ and holding for 3 hours, a 2-EHA solution of an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 133 parts of 2-EHA, 7 parts of HEA and 1009 parts of LUNA were added, and the mixture was incubated at 70 ℃ for 2 hours to confirm completion of the reaction by NCO value measurement, whereby a 2-EHA solution of polyurethane (A-2) having a weight average molecular weight of 35,000 and an average number of acryloyl groups of 1.0 was obtained. The introduction rate of the skeleton derived from the component (a3) was 50 mol%, and the introduction rate of the skeleton derived from the component (a4) was 50 mol%.
Production example 3
Into a reaction apparatus equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 561 parts of an aliphatic polyester diol having a number average molecular weight of 2,000 (product name "PLACCEL L220 AL" manufactured by Daicel, Ltd.), 63 parts of HDI, 217 parts of 2-EHA, 0.4 parts of MQ and 0.1 part of stannous octoate were charged, and after heating to 60 ℃ and heat preservation for 3 hours, a 2-EHA solution of an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 133 parts of 2-EHA, 13 parts of HEA, and 10013 parts of LUNA were added thereto, and the mixture was incubated at 70 ℃ for 2 hours to confirm completion of the reaction by NCO value measurement, whereby a 2-EHA solution of polyurethane (A-3) having a weight average molecular weight of 38,000 and an average number of acryloyl groups of 1.16 was obtained. The introduction rate of the skeleton derived from the component (a3) was 58 mol%, and the introduction rate of the skeleton derived from the component (a4) was 42 mol%.
Production example 4
PTMG2000544 parts, isophorone diisocyanate 81 parts, 2-EHA217 parts, MQ0.4 parts and stannous octoate 0.1 parts are added into a reaction device provided with a cooling pipe, a stirrer and a nitrogen introducing pipe, and after the temperature is raised to 60 ℃ and the temperature is kept for 3 hours, the 2-EHA solution of isocyanate group terminated urethane prepolymer as an intermediate is obtained. Subsequently, 133 parts of 2-EHA, 12 parts of HEA, and 10012 parts of LUNA were added thereto, and the mixture was incubated at 70 ℃ for 2 hours to confirm completion of the reaction by NCO value measurement, whereby a 2-EHA solution of polyurethane (A-4) having a weight average molecular weight of 37,000 and an average number of acryloyl groups of 1.16 was obtained. The introduction rate of the skeleton derived from the component (a3) was 58 mol%, and the introduction rate of the skeleton derived from the component (a4) was 42 mol%.
Production example 5
PTMG2000552 parts, HDI 62 parts, 2-EHA217 parts, MQ0.4 parts and stannous octoate 0.1 parts were added to a reaction apparatus equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and after heating to 60 ℃ and heat preservation for 3 hours, a 2-EHA solution of an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 133 parts of 2-EHA, 23 parts of 2-hydroxy-3-acryloyloxypropyl methacrylate (product name "Lightester (ライトエステル) G-201P" manufactured by Kyoeisha Co., Ltd.) and 10013 parts of LUNA were added, and the mixture was incubated at 70 ℃ for 2 hours to confirm completion of the reaction by NCO value measurement, whereby a 2-EHA solution of polyurethane (A-5) having a weight average molecular weight of 36,000 and an average number of acryloyl groups of 2.32 was obtained. The introduction rate of the skeleton derived from the component (a3) was 73 mol%, and the introduction rate of the skeleton derived from the component (a4) was 27 mol%.
Production example 6
PTMG2000560 parts, HDI 63 parts, 2-EHA217 parts, MQ0.4 parts and stannous octoate 0.1 parts were added to a reaction apparatus equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and after heating to 60 ℃ and heat preservation for 3 hours, a 2-EHA solution of an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 133 parts of 2-EHA, 5 parts of HEA, and 10023 parts of LUNA were added thereto, and the mixture was incubated at 70 ℃ for 2 hours to confirm completion of the reaction by NCO value measurement, whereby a 2-EHA solution of polyurethane (A-6) having a weight average molecular weight of 36,000 and an average number of acryloyl groups of 0.5 was obtained. The introduction rate of the skeleton derived from the component (a3) was 25 mol%, and the introduction rate of the skeleton derived from the component (a4) was 75 mol%.
Production example 7
PTMG2000540 parts, HDI 63 parts, 2-EHA217 parts, MQ0.4 parts and stannous octoate 0.1 parts were added to a reaction apparatus equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and after heating to 60 ℃ and heat preservation for 3 hours, a 2-EHA solution of an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 133 parts of 2-EHA, 36 parts of HEA, and 10012 parts of LUNA were added thereto, and the mixture was incubated at 70 ℃ for 2 hours to confirm completion of the reaction by NCO value measurement, whereby a 2-EHA solution of polyurethane (A-7) having a weight average molecular weight of 36,000 and an average number of acryloyl groups of 3.48 was obtained. The introduction rate of the skeleton derived from the component (a3) was 58 mol%, and the introduction rate of the skeleton derived from the component (a4) was 42 mol%.
Production example 8
PTMG2000560 parts, HDI 63 parts, 2-EHA217 parts, MQ0.4 parts and stannous octoate 0.1 parts were added to a reaction apparatus equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and after heating to 60 ℃ and heat preservation for 3 hours, a 2-EHA solution of an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 133 parts of 2-EHA, 13 parts of HEA, and 16 parts of 1-hydroxycyclohexyl phenyl ketone (manufactured by DKSH Japan, trade name: LUNA200) were added thereto, and the mixture was incubated at 70 ℃ for 2 hours to confirm completion of the reaction by NCO value measurement, whereby a 2-EHA solution of polyurethane (A-8) having a weight average molecular weight of 36,000 and an average number of acryloyl groups of 1.16 was obtained. The introduction rate of the skeleton derived from the component (a3) was 58 mol%, and the introduction rate of the skeleton derived from the component (a4) was 42 mol%.
Production example 9
PTMG2000561 parts, HDI 63 parts, lauryl acrylate (hereinafter referred to as LA)217 parts, MQ0.4 parts and stannous octoate 0.1 parts were charged into a reaction apparatus equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and the mixture was heated to 60 ℃ and kept warm for 3 hours to obtain an LA solution of an isocyanate group-terminated urethane prepolymer as an intermediate. Then, 133 parts of LA, 13 parts of HEA, and 10013 parts of LUNA were added, and the mixture was incubated at 70 ℃ for 2 hours to confirm completion of the reaction by NCO value measurement, whereby a LA solution of polyurethane (A-9) having a weight average molecular weight of 36,000 and an average number of acryloyl groups of 1.16 was obtained. The introduction rate of the skeleton derived from the component (a3) was 58 mol%, and the introduction rate of the skeleton derived from the component (a4) was 42 mol%.
Comparative production example 1
PTMG2000565 parts, HDI 63 parts, 2-EHA217 parts, MQ0.4 parts and stannous octoate 0.1 parts were added to a reaction apparatus equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and after heating to 60 ℃ and heat preservation for 3 hours, a 2-EHA solution of an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 133 parts of 2-EHA and 22 parts of HEA were added, and the mixture was incubated at 70 ℃ for 2 hours to confirm completion of the reaction by NCO value measurement, whereby a 2-EHA solution of polyurethane (E-1) having a weight average molecular weight of 36,000 and an average number of acryloyl groups of 2.0 was obtained. The introduction rate of the skeleton derived from the component (a3) was 100 mol%.
Comparative production example 2
PTMG2000557 parts, HDI 62 parts, 2-EHA217 parts, MQ0.4 parts and stannous octoate 0.1 parts were added to a reaction apparatus equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and after heating to 60 ℃ and heat preservation for 3 hours, a 2-EHA solution of an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 133 parts of 2-EHA and 10030 parts of LUNA were added, and the mixture was incubated at 70 ℃ for 2 hours to confirm completion of the reaction by NCO value measurement, whereby a 2-EHA solution of polyurethane (E-2) having a weight average molecular weight of 36,000 and an average number of acryloyl groups of 0 was obtained. The introduction rate of the skeleton derived from the component (a4) was 100 mol%.
Table 1 shows the introduction rates of the skeletons derived from the component (a3) and the component (a4) in production examples 1 to 9, comparative production example 1, and comparative production example 2.
[ Table 1]
Figure BDA0002426570810000181
Example 1
The ultraviolet-curable adhesive composition for protective films was obtained by mixing the component (A-1), 2-EHA as the component (B), a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as the component (C) (trade name "NK ester A-9550W", manufactured by Ninghamu chemical industries, Ltd.), dioctyl adipate (hereinafter referred to as DOA) as the component (D) and 1-hydroxycyclohexyl phenyl ketone (trade name "LUNA 200", manufactured by DKSH Japan, Ltd.) (hereinafter referred to as LUNA200) as a photopolymerization initiator at the content ratios shown in Table 2.
Examples 2 to 23 and comparative examples 1 to 9
In the same manner as in example 1, ultraviolet-curable adhesive compositions for protective films were obtained according to the compositions shown in table 2.
The following experiment was performed on the ultraviolet-curable adhesive composition for a protective film of each example and comparative example.
The adhesive composition of example 1 was applied to one surface of a 50 μm-thick polyester film (trade name: "Cosmoshine (コスモシャイン) a 4100", manufactured by eastern incorporated by reference) (hereinafter referred to as "a 4100") using a comma coater so as to form a film thickness of 100 μm, a 38 μm-thick light release treated polyester film (trade name: "SP-PET-01-38 BU", manufactured by PANAC (パナック) ") (hereinafter referred to as" release PET ") was attached to the applied layer, and then a 120W/cm high-pressure mercury lamp (manufactured by yazaki electric corporation) was used to irradiate ultraviolet rays from the release PET side so that the cumulative light amount was 900mJ/cm2A protective sheet comprising a peeled PET/cured product layer (100 μm)/A4100 was produced. A protective plate was produced in the same manner as for the adhesive compositions of examples 2 to 23 and comparative examples 1 to 9.
< adhesion >
The peeled PET of the protective sheet was peeled off, and the resultant was bonded to a glass plate with a 2kg roll to prepare a laminate (A4100/cured product layer/glass plate), which was left to stand at 25 ℃ and 50% humidity for 24 hours. Next, the laminate was peeled from the glass plate at a speed of 300 mm/min in a 180 ℃ direction using a single column type Material testing machine STA-1225 (manufactured by Tokusho A & D (エー, アンド, デイ)), and the adhesive force (unit: mN/25mm) was measured. The smaller the value, the lower the adhesion. The adhesive strength was as good as 300mN/25mm or less. The results are shown in Table 2 (the same applies hereinafter).
< self-adsorption Property >
A50 mm. times.50 mm measurement sample was cut out from the above-mentioned protective plate. The peeled PET was peeled from the measurement sample in an atmosphere at a temperature of 23 ℃ and a humidity of 50%, and then both ends of the plate were held with both hands while the center portion of the exposed surface of the cured product layer was brought into contact with the glass plate, and then both hands were released. The time until all of the cured product layers were in close contact with the glass plate by the weight of the plate was measured, and the self-adhesion to the glass plate was evaluated according to the following criteria. The shorter the time taken until the glass plate was brought into close contact with the member, the more easily the member was adhered to the member, and the self-adhesive property was excellent.
(evaluation criteria)
Very good: less than 5 seconds
O: more than 5 seconds and less than 10 seconds
And (delta): more than 10 seconds and less than 60 seconds
X: over 60 seconds
< cutting Property >
The sample obtained by peeling the peeled PET from the protective plate was cut with the cured product layer facing upward on a cutter pad using a commercially available cutter, and the cross section was observed at 400 times using a laser microscope (ultra-deep color 3D shape measuring microscope, manufactured by Keyence (キーエンス) corporation). The evaluation criteria are as follows.
(evaluation criteria)
O: the cured layer has no roughness (unevenness) in cross section and no fine debris of the adhesive (see fig. 1).
And (delta): the cured layer is slightly rough (uneven) in cross section or has a fine smear of adhesive (see fig. 2).
X: the cured layer has a rough (uneven) cross section or has a fine powder of the adhesive up to the surface (see fig. 3).
In fig. 1 to 3, the lower layer is a cured product layer, and the upper layer is an a4100 layer.
[ Table 2]
Figure BDA0002426570810000211
The abbreviations for the ingredients in table 2 refer to the following compounds.
< ingredient (A) >
A-1: preparation example 1 polyurethane
A-2: preparation example 2 polyurethane
A-3: preparation example 3 polyurethane
A-4: preparation example 4 polyurethane
A-5: preparation example 5 polyurethane
A-6: preparation example 6 polyurethane
A-7: production example 7 polyurethane
A-8: production example 8 polyurethane
A-9: production example 9 polyurethane
E-1: comparative production example 1 polyurethane
E-2: comparative production example 2 polyurethane
< ingredient (B) >
2-EHA: 2-ethylhexyl acrylate (number of carbon atoms in alkyl group: 8)
BA: n-butyl acrylate (number of carbon atoms in alkyl group: 4)
NOAA: n-octyl acrylate (number of carbon atoms in alkyl group: 8)
LA: n-lauryl acrylate (number of carbon atoms in alkyl group: 12)
ISTA: isostearyl acrylate (number of carbon atoms in alkyl group: 18)
VA: behenyl acrylate (carbon number of alkyl: 22)
< ingredient (C) >
C-1: trade name "NK ester A-9550W", a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Ningmura chemical industries, Ltd
C-2: trade name "ARONIX (アロニックス) M-306", a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Toyo Synthesis
C-3: the trade name is "Viscoat (ビスコート) #335 HP", tetraethylene glycol diacrylate, manufactured by Osaka organic chemical industry Co., Ltd
< ingredient (D) >
DOA: dioctyl adipate
D620: trade name "D-620", adipic acid polyester (Mw. -800 blend), Mitsubishi ケミカル
RS-700: trade name "アデカサイザー RS-700", polyether ester (Mw. about 550), manufactured by ADEKA
ARUFON: trade name "ARUFON UP 1010", liquid acrylic Polymer (Mw.1700), manufactured by Toyo Seiya Kabushiki Kaisha
KE-100: the product name "Pinecrystal (パインクリスタル) KE-100", disproportionated rosin ester, manufactured by Mitsukawa chemical industry Co., Ltd.

Claims (8)

1. An ultraviolet-curable adhesive composition for a protective film, comprising:
a polyurethane (a) which is a reactant of a polyol (a1), a polyisocyanate (a2), a hydroxyl group-containing (meth) acrylate (a3), and a hydroxyl group-containing photopolymerization initiator (a 4);
an alkyl mono (meth) acrylate (B) having an alkyl group with 6 to 18 carbon atoms;
a polyfunctional (meth) acrylate (C);
a plasticizer (D) which is a mixture of a plasticizer,
in the component (a), the introduction rate of the skeleton derived from the component (a3) and the introduction rate of the skeleton derived from the component (a4) are 5 to 95 mol% with respect to the blocked isocyanate groups of the urethane prepolymer composed of the component (a1) and the component (a2), respectively.
2. The ultraviolet-curable adhesive composition for protective films according to claim 1, wherein the component (a1) is a polyether polyol and/or a polyester polyol.
3. The ultraviolet-curable adhesive composition for protective films according to claim 1 or 2, wherein the component (a3) is a hydroxyl group-containing mono (meth) acrylate and/or a hydroxyl group-containing di (meth) acrylate.
4. The ultraviolet-curable adhesive composition for protective films according to any one of claims 1 to 3, wherein the total amount of the component (A), the component (B) and the component (C) is 100% by mass, the component (A) is 20 to 84% by mass, the component (B) is 15 to 79% by mass, and the component (C) is 1 to 65% by mass.
5. The ultraviolet-curable adhesive composition for protective films according to any one of claims 1 to 4, wherein the component (D) comprises at least 1 selected from the group consisting of saturated fatty acid esters, nonreactive ester polymers, acrylic polymers and rosins containing no conjugated bonds.
6. The ultraviolet-curable adhesive composition for protective films according to any one of claims 1 to 5, wherein the component (D) is 1 to 50% by mass based on 100% by mass of the total of the components (A), (B) and (C).
7. A cured product of the ultraviolet-curable adhesive composition for protective films according to any one of claims 1 to 6.
8. A protective plate having a layer comprising the cured product according to claim 7 on at least one surface of a member.
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