JP6953779B2 - An active energy ray-curable adhesive composition for polycarbonate-based members and an adhesive for polycarbonate-based members using the same. - Google Patents

Description

The present invention relates to an active energy ray-curable adhesive composition for a polycarbonate-based member. Specifically, the present invention can obtain an adhesive layer having excellent adhesiveness to a polycarbonate-based resin and excellent hardness, and has excellent coatability. It also relates to an excellent adhesive composition.

A transparent base material is required for optical devices such as touch panels and optical members such as optical recording media, and glass base materials have been used conventionally. However, in recent years, from the viewpoint of impact resistance and weight reduction, Highly transparent plastics are becoming widely used instead of glass. In particular, polymethylmethacrylate is mentioned as a typical transparent base material used for a display such as a liquid crystal display. However, the polymethylmethacrylate base material has problems such as warpage due to moisture absorption and insufficient heat resistance. Therefore, in applications that require durability, polycarbonate substrates with excellent transparency, heat resistance, impact resistance, dimensional stability, etc. are increasingly being used, and optical properties such as adhesive strength and transparency to polycarbonate are increasing. There is a demand for an adhesive having excellent active energy ray curability.

Further, depending on the application, the hardness of the adhesive layer itself is also required. As an example, in the adhesion between the hard coat film to which functionality has been imparted and the polycarbonate base material, if the film thickness of the hard coat film is thin, it is greatly affected by the hardness of the underlying adhesive layer. In order to bring out the hardness, an active energy ray-curable adhesive having a higher hardness is required.

It is known that an adhesive made of a urethane (meth) acrylate-based compound can be used as an adhesive for an optical member that requires such physical properties. For example, Patent Document 1 describes (A) (meth). A (meth) acrylate-based compound containing an acrylate monomer, a (B) urethane-based (meth) acrylate oligomer, and any one selected from (C) an acrylamide derivative, (D) a silane compound, and (E) an organic phosphorus compound. It has been shown that the polycarbonate resin laminate made of the adhesive composition is excellent in transparency, adhesive strength, heat resistance, moisture resistance and bending workability. Further, Patent Document 2 describes urethane (meth) acrylate obtained by reacting (a1) polycarbonate diol, (a2) diisocyanate compound, and (a3) hydroxyl group-containing (meth) acrylic acid ester with other acrylic acids. It has been shown that an active energy ray-curable composition containing an ester has both strong elongation characteristics and transparency, and is useful as a composition for coating or molding (adhering) a plastic film, an optical disk, or the like.

JP-A-2009-274256 Japanese Unexamined Patent Publication No. 2005-68331

However, the techniques disclosed in Patent Documents 1 and 2 cannot satisfy both adhesiveness and hardness, and the adhesive layer turns yellow under high temperature conditions, and transparency cannot be obtained. There was also the problem.

Therefore, it is an object of the present invention to provide an active energy ray-curable adhesive composition capable of obtaining an adhesive layer having excellent adhesiveness to a polycarbonate-based member and excellent hardness under such a background. Is to be.

However, as a result of intensive studies in view of such circumstances, the present inventors have used acryloylmorpholine as an active energy ray-curable monomer in the active energy ray-curable adhesive composition, and urethane (meth) acrylate having a carbonate structure. We have found that by using a system compound in combination, an adhesive composition capable of obtaining an adhesive layer having excellent adhesiveness to a polycarbonate resin and also having excellent hardness after curing can be obtained, and the present invention has been completed. ..

This is a polycarbonate-based member by using acryloylmorpholin, which has a high glass transition temperature and high cohesive force when made into a homopolymer, and a urethane (meth) acrylate-based compound having a carbonate structure having excellent hardness when cured. It is presumed that an active energy ray-curable adhesive composition satisfying the hardness as well as the adhesiveness of the above can be obtained.

That is, the gist of the present invention relates to an active energy ray-curable adhesive composition for a polycarbonate-based member containing acryloyl morpholine and a urethane (meth) acrylate-based compound (A) having a carbonate structure.
The present invention also provides an adhesive for polycarbonate-based members using the above-mentioned active energy ray-curable adhesive composition.

The active energy ray-curable adhesive composition of the present invention is particularly excellent in adhesiveness to a polycarbonate-based resin, and is also excellent in coatability and hardness of the adhesive layer after curing in a well-balanced manner. It is useful as an adhesive for polycarbonate-based members that adheres a member made of (polycarbonate film or the like) to another member. In addition, it is also excellent in adhesiveness to various resin members other than polycarbonate-based members.

Further, in the present invention, by further reducing the content of the metal component in the active energy ray-curable adhesive composition to a specific value or less, an adhesive layer having excellent transparency even under heat-resistant conditions can be obtained. Can be done.

Hereinafter, the present invention will be described in detail, but these are examples of desirable embodiments.
In the present invention, (meth) acrylic acid refers to acrylic acid or methacrylic acid, (meth) acrylic refers to acrylic or methacrylic acid, (meth) acryloyl refers to acryloyl or methacryloyl, and (meth) acrylate refers to acrylate or methacrylic acid. It means each methacrylate.

The active energy ray-curable adhesive composition for a polycarbonate-based member of the present invention uses acryloyl morpholine as an active energy ray-curable monomer and a urethane (meth) acrylate-based compound having a carbonate structure as a urethane (meth) acrylate-based compound. A) (hereinafter, "may be referred to as" urethane (meth) acrylate compound (A) ") is used.

[Urethane (meth) acrylate compound (A)]
The urethane (meth) acrylate-based compound (A) of the present invention is a compound having a carbonate structure.
The urethane (meth) acrylate-based compound (A) of the present invention may be any compound having a carbonate structure, but preferably, the urethane (meth) acrylate-based compound (A) is a polyol having a carbonate structure. It has a structure derived from it, and is obtained as a reaction product of, for example, a polyvalent isocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2), and a polycarbonate-based polyol (a3). Is particularly preferable.

Examples of the polyvalent isocyanate-based compound (a1) include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylenedi isocyanate, and naphthalene. Aromatic polyisocyanates such as diisocyanates; aliphatic polyisocyanates such as pentamethylene diisocyanates, hexamethylene diisocyanates, trimethylhexamethylene diisocyanates, lysine diisocyanates and lysine triisocyanates; isophorone diisocyanates, 1,3-bis (isocyanato) cyclohexane, 1 , 4-Bis (isocyanato) cyclohexane, norbornene diisocyanate, alicyclic polyisocyanate such as 4,4'-dicyclohexylmethane diisocyanate, or trimeric compound or multimer compound of these polyisocyanates; allophanate type polyisocyanate, bullet type Examples include polyisocyanate.
These can be used alone or in combination of two or more.

Among these, aliphatic diisocyanates and alicyclic diisocyanates are preferably used because they cause less yellowing, and isophorone diisocyanates and 1,3-bis (isophorone diisocyanates) are particularly preferable because they are excellent in reactivity and versatility. Isocyanato) Cyclohexane and 4,4'-dicyclohexylmethane diisocyanate are used.

Examples of the hydroxyl group-containing (meth) acrylate compound (a2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). ) Acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, caprolactone-modified 2-hydroxyethyl ( Meta) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified-glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl A hydroxyl group-containing (meth) acrylate-based compound containing one ethylenically unsaturated group such as (meth) acrylate; an ethylenically unsaturated group such as glycerindi (meth) acrylate and 2-hydroxy-3-acryloyl-oxypropyl methacrylate. Pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) Examples thereof include hydroxyl group-containing (meth) acrylate compounds containing three or more ethylenically unsaturated groups such as acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, and ethylene oxide-modified dipentaerythritol penta (meth) acrylate.
These hydroxyl group-containing (meth) acrylate compounds (a2) can be used alone or in combination of two or more.

Among these, a hydroxyl group-containing (meth) acrylate-based compound having one ethylenically unsaturated group is preferable in that it has excellent adhesive strength when used as an adhesive, and 2-hydroxyethyl (meth) acrylate is particularly preferable. Hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate are more preferable. 2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are excellent in reactivity and versatility.

Examples of the polycarbonate-based polyol (a3) include a reaction product of a polyhydric alcohol and a carbonic acid ester, a reaction product of a polyhydric alcohol and a phosgen, and a ring-opening polymer of a polyhydric alcohol and a cyclic carbonate ester (alkylene carbonate, etc.). Can be mentioned.

Examples of the polyhydric alcohol used as a raw material for the polycarbonate-based polyol (a3) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-tetramethylenediol, and 1,3. -Tetramethylene diol, 2-methyl-1,3-trimethylene diol, 1,4-butane diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1, 5-Pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.) , Glycols (such as xylitol and sorbitol).

Examples of the alkylene carbonate used as a raw material for the polycarbonate-based polyol (a3) include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate and the like.

Among these, a polycarbonate-based polyol having a linear structure (a structure that does not contain branched polycarbonate chains) is preferable from the viewpoint of adhesiveness to the polycarbonate-based resin base material.

The polycarbonate-based polyol compound (a3) can be used alone or in combination of two or more.
In the present invention, the polycarbonate-based polyol compound (a3) may be a compound having a carbonate bond in the molecule and having a hydroxyl group at the end, and may have an ester bond together with the carbonate bond.

In the present invention, a polyol-based compound other than the polycarbonate-based polyol compound (a3) can be used in combination as long as the effect of the present invention is not impaired, and examples of other polyol-based compounds include polyether-based polyols and polyesters. Examples thereof include based polyols, polyolefin-based polyols, (meth) acrylic-based polyols, and polysiloxane-based polyols.

The number average molecular weight of the polycarbonate-based polyol (a3) used in the present invention is preferably 300 to 10,000, particularly preferably 400 to 5,000, and even more preferably 500 to 2,000. If the number average molecular weight is too small, the molecular weight of the obtained urethane (meth) acrylate compound becomes small, and the coatability of the adhesive composition tends to be lowered, or sufficient adhesive strength tends not to be obtained. On the other hand, if it is too large, the molecular weight of the obtained urethane (meth) acrylate compound becomes large, and the viscosity tends to be high to reduce the coatability, or sufficient hardness cannot be obtained after the active energy ray curing.
The above number average molecular weight is calculated from the hydroxyl value of each polyol.

The number of hydroxyl groups contained in the polycarbonate-based polyol (a3) is preferably 2 to 5, particularly preferably 2 to 3, and even more preferably 2. If the number of hydroxyl groups is too large, gelation tends to occur during the reaction.

The hydroxyl value of the polycarbonate-based polyol (a3) is preferably 10 to 400 mgKOH / g, particularly preferably 20 to 300 mgKOH / g, and even more preferably 50 to 250 mgKOH / g. If the hydroxyl value is too high, the urethane (meth) acrylate compound tends to have a low molecular weight and the adhesive force with the adherend tends to decrease, and if it is too low, the obtained urethane (meth) acrylate compound and the urethane (meth) acrylate compound contained therein are contained. Since the adhesive composition becomes highly viscous and the coatability is lowered, the workability tends to be lowered.
The hydroxyl value can be measured based on JIS K 0070-1992.

Further, in the present invention, it is preferable to use a polycarbonate-based polyol (a3) having a low metal content concentration, specifically, 100 ppm or less, particularly preferably 50 ppm or less, still more preferably 20 ppm. It is as follows. If the content concentration is too high, yellowing of the obtained active energy ray-curable adhesive composition and the cured product (adhesive layer) tends to occur easily.
The metal content concentration is a value measured by an ICP-AES analysis method.
The lower limit of the metal content concentration is usually 1 ppm.

The urethane (meth) acrylate compound (A) used in the present invention includes, for example, (1) the above-mentioned polyvalent isocyanate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2), and a polycarbonate-based polyol (a3). ) Is collectively charged into a reactor, and (2) a hydroxyl group-containing (meth) acrylate-based reaction product obtained by reacting a polyvalent isocyanate compound (a1) with a polycarbonate-based polyol (a3) in advance. A method for reacting the compound (a2), (3) a polycarbonate-based polyol (a3) is added to a reaction product obtained by reacting a polyvalent isocyanate-based compound (a1) with a hydroxyl group-containing (meth) acrylate-based compound (a2) in advance. ), Etc., but the method (2) is preferable from the viewpoint of reaction stability and reduction of by-products.

A known reaction means can be used for the reaction between the polyisocyanate compound (a1) and the polycarbonate-based polyol (a3). At that time, for example, the molar ratio of the isocyanate group in the polyhydric isocyanate compound (a1) to the hydroxyl group in the polycarbonate-based polyol compound (a3) is usually about 2n: (2n-2) (n is an integer of 2 or more). A terminal isocyanate group-containing urethane (meth) acrylate-based compound in which an isocyanate group remains can be obtained, and after the compound is obtained, an addition reaction with the hydroxyl group-containing (meth) acrylate-based compound (a2) is carried out. To enable.
The reaction ratio (molar ratio) of the isocyanate group in the polyhydric isocyanate group (a1) to the hydroxyl group of the polycarbonate-based polyol (a3) is the isocyanate group of (a1): the hydroxyl group of (a3) = 2: 1 to 6: It is preferably 5, and more preferably 2: 1 to 3: 2.

The reaction product obtained by reacting the polyhydric isocyanate compound (a1) with the polycarbonate-based polyol compound (a3) in advance and the hydroxyl group-containing (meth) acrylate-based compound (a2) are also known for an addition reaction. Reaction means can be used.

The reaction molar ratio of the reaction product obtained by reacting the polyvalent isocyanate compound (a1) with the polycarbonate polyol compound (a3) in advance and the hydroxyl group-containing (meth) acrylate compound (a2) is, for example, many. When the valent isocyanate compound (a1) has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (a2) has one hydroxyl group, the reaction product: the hydroxyl group-containing (meth) acrylate compound (a2). ) Is about 1: 2, the polyvalent isocyanate compound (a1) has three isocyanate groups, and the hydroxyl group-containing (meth) acrylate compound (a2) has one hydroxyl group. The hydroxyl group-containing (meth) acrylate compound (a2) is about 1: 3.

In the addition reaction between this reaction product and the hydroxyl group-containing (meth) acrylate compound (a2), urethane is terminated when the residual isocyanate group content of the reaction system becomes 0.3% by weight or less. The (meth) acrylate compound (A) is obtained.

At the time of the above reaction, the reaction temperature is usually 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction time is usually 2 to 30 hours, preferably 3 to 20 hours.

In the reaction between the polyvalent isocyanate-based compound (a1) and the polycarbonate-based polyol (a3), and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate-based compound (a2), a catalyst is used for the purpose of promoting the reaction. As such a catalyst, for example, an organic metal compound such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, zinc octate, tin octate, tin octylate, cobalt naphthenate, etc. Metal salts such as bismuth chloride and bismuth chloride, triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N , N', N'-tetramethyl-1,3-butanediamine, N-ethylmorpholin and other amine-based catalysts, bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc., as well as dibutyl bismuth dilaurate, dioctyl bismuth. Organic bismuth compounds such as dilaurate, 2-ethylhexanoic acid bismuth salt, naphthenic acid bismuth salt, isodecanoic acid bismuth salt, neodecanoic acid bismuth salt, lauric acid bismuth salt, maleic acid bismuth salt, stearate bismuth salt, oleate bismuth salt. , Bismuth linoleic acid bismuth salt, bismuth acetate salt, bismuth bismuth neodecanoate, bismuth dysalicylic acid bismuth salt, bismuth organic acid such as bismuth dicalcified acid bismuth salt, inorganic zirconium, organic zirconium, zirconium such as zirconium alone Examples include those in which two or more types of catalysts such as a system catalyst and zinc 2-ethylhexanoate / zirconium tetraacetylacetonate are used in combination. Among them, dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene. Is preferable. In addition, these catalysts can be used alone or in combination of two or more.

Further, in the reaction between the polycarbonate-based polyol compound (a3) and the polyvalent isocyanate-based compound (a1), and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate-based compound (a2), isocyanate is required. Organic solvents that do not have functional groups that react with groups, such as esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene are used. You may.

Thus, the urethane (meth) acrylate-based compound (A) used in the present invention is produced.
The weight average molecular weight of the urethane (meth) acrylate compound (A) is 5000 to 14000. If the weight average molecular weight is too small, the coatability of the adhesive composition tends to be deteriorated, or it tends to be difficult to obtain sufficient adhesive force, and if it is too large, the viscosity becomes high and handling and coating become difficult. , The active energy ray curability tends to decrease and sufficient coating hardness cannot be obtained.

The above weight average molecular weight is a weight average molecular weight converted to standard polystyrene molecular weight, and is subjected to high performance liquid chromatography (“ACQUITY APC system” manufactured by Waters), column: ACQUITY APC XT 450 × 1, ACQUITY APC XT. It is measured by using four series of 200 × 1 and ACQUITY APC XT 45 × 2.

The viscosity (60 ° C.) of the urethane (meth) acrylate compound (A) is preferably 5,000 to 500,000 mPa · s, particularly preferably 10,000 to 200,000 mPa · s, and even more preferably 10,000 to 200,000 mPa · s. Is 20,000 to 100,000 mPa · s. If the viscosity is too high, it tends to be difficult to handle and coat, and if it is too low, the coatability tends to decrease.
The viscosity is the viscosity measured using an E-type viscometer.

Further, the metal content concentration of the urethane (meth) acrylate compound (A) is preferably 50 ppm or less, particularly preferably 40 ppm or less, and further preferably 20 ppm or less. If the metal content is too high, the cured product (adhesive layer) tends to turn yellow. The lower limit of the metal content concentration is usually 1 ppm.

[Active energy ray-curable adhesive composition]
By containing acryloyl morpholine and the urethane (meth) acrylate compound (A) having the above polycarbonate structure, the active energy ray-curable adhesive composition of the present invention can be obtained.

The content ratio (weight ratio) of acryloyl morpholine and urethane (meth) acrylate compound (A) in the active energy ray-curable adhesive composition is acryloyl morpholine: urethane (meth) acrylate compound (A) = 90. : 10 to 50:50.
If the content ratio of the urethane (meth) acrylate compound (A) having a polycarbonate structure is too large, the viscosity of the adhesive composition becomes high and it becomes difficult to handle, the coatability deteriorates, and it is sufficient after the active energy ray curing. Hardness and adhesive strength tend to be lost. On the other hand, if the amount is too small, the viscosity of the adhesive composition is low and the coatability tends to be lowered, or sufficient curability tends not to be obtained.

The active energy ray-curable adhesive composition of the present invention preferably further contains a photopolymerization initiator (B) in order to efficiently cure with the active energy rays.
The photopolymerization initiator (B) is not particularly limited as long as it generates radicals by the action of light, and is, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. , Benzyldimethylketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1 -On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer, 1-[ 4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) ) -Phenyl] -Phenyl} -2-Methyl-Propane-1-one and other acetophenones; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoins; benzophenone, o-benzoyl benzo Methyl acid, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-Benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethaminium bromide, (4-benzoylbenzyl) benzophenones such as trimethylammonium chloride; 2-isopropyl Thioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H Thioxanthones such as −thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, Examples thereof include acylphosphon oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; and the like. These photopolymerization initiators may be used alone or in combination of two or more.

In addition, as an auxiliary agent for these photopolymerization initiators, for example, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, etc. Ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2, It is also possible to use 4-diisopropylthioxanson or the like in combination. These auxiliaries can also be used alone or in combination of two or more.

The content of the photopolymerization initiator (B) is the total of acryloyl morpholine and the urethane (meth) acrylate compound (A) (when the following ethylenically unsaturated compound (C) is contained, the content is further (C). It is preferably 0.1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, and further preferably 2 to 5 parts by weight with respect to 100 parts by weight. If the content is too small, the curing rate tends to decrease or the adhesive strength tends to decrease, and if it is too large, the curability does not improve and yellowing tends to occur under high temperature conditions.

Further, in the active energy ray-curable adhesive composition of the present invention, an ethylenically unsaturated compound (C) other than acryloylmorpholine may be used as the active energy ray-curable monomer, and the ethylenically unsaturated compound (C) may be used. ) Examples include an ethylenically unsaturated compound having one ethylenically unsaturated group and an ethylenically unsaturated compound having two or more ethylenically unsaturated groups. The ethylenically unsaturated compound (C) may be used alone or in combination of two or more.

The content of the ethylenically unsaturated compound (C) is 70% by weight or less based on 100 parts by weight of the total of the acryloyl morpholine, the urethane (meth) acrylate compound (A) and the ethylenically unsaturated compound (C). It is preferably 50% by weight or less, more preferably 30% by weight or less.
If the content is too large, the adhesiveness to the polycarbonate-based substrate tends to decrease.

Examples of the ethylenically unsaturated compound having one ethylenically unsaturated group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth). ) Acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) ) Acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, phenolethylene oxide modification ( Meta) acrylate, nonylphenol propylene oxide modified (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, butoxyethyl (meth) ) Acrylate, N-vinylpyrrolidone, 2-vinylpyridine, glycidyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl) -2-Ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) methyl (meth) acrylate, γ-butyrolactone (meth) acrylate , Trimethylol propane (formal) (meth) acrylate, styrene, vinyl toluene, chlorostyrene, α-methylstyrene, acrylonitrile, vinyl acetate, allyl (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate monoester, etc. Can be mentioned.

In addition to the above, a Michael adduct of acrylic acid or a 2-acryloyloxyethyl dicarboxylic acid monoester can also be mentioned. Examples of the Michael adduct of acrylic acid include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimmer, and methacrylic acid trimmer. , Acrylic acid tetramer, methacrylic acid tetramer and the like. Examples of the 2-acryloyloxyethyl dicarboxylic acid monoester, which is a carboxylic acid having a specific substituent, include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyloxyethyl. Examples thereof include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Further, oligoester acrylate can also be mentioned.

Examples of the ethylenically unsaturated compound having two or more ethylenically unsaturated groups include a bifunctional (meth) acrylate-based monomer and a trifunctional or higher-functional (meth) acrylate-based monomer, and a bifunctional (meth) acrylate-based monomer. Examples of the monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene glycol di (meth). ) Acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified bisphenol A type di (meth) acrylate, propylene oxide-modified bisphenol A type di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-hexanediol ethylene oxide-modified di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, diglycidyl phthalate (meth) Examples thereof include acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, and 2- (meth) acryloyloxyethyl acid phosphate diester.

The trifunctional or higher functional (meth) acrylate-based monomer may be a monomer containing three or more ethylenically unsaturated groups, for example, trimethylolpropantri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and di. Pentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylol propane, isocyanurate ethylene oxide-modified triacrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified pentaerythritol tetra (meth) acrylate, Examples thereof include caprolactone-modified dipentaerythritol hexa (meth) acrylate and caprolactone-modified pentaerythritol tetra (meth) acrylate.

The active energy ray-curable adhesive composition of the present invention includes acryloylmorpholine, a urethane (meth) acrylate compound (A) having a polycarbonate structure, a photopolymerization initiator (B), and an ethylenically unsaturated compound (C). It is possible to add a resin such as an acrylic resin or a polyurethane compound, or an inorganic particle such as silica gel, if necessary. In addition, known general additives such as antioxidants, flame retardants, antistatic agents, fillers, leveling agents, stabilizers, reinforcing agents, and matting agents may be contained as long as the effects of the present invention are not impaired. It is possible. Further, as the cross-linking agent, an epoxy compound, an aziricin compound, a melamine compound, an isocyanate compound, a chelate compound and the like can be contained.

Further, the active energy ray-curable adhesive composition of the present invention can contain a polythiol compound from the viewpoint of suppressing unreacted components and improving the adhesive force.
The polythiol compound is not particularly limited, but a compound having 2 to 6 mercapto groups in the molecule is preferable, for example, aliphatic polythiols such as alkanedithiol having about 2 to 20 carbon atoms, aromatics such as xylylene dithiol, and the like. Polythiols, polythiols formed by substituting the halogen atom of the halohydrin adduct of alcohols with a mercapto group, polythiols composed of hydrogen sulfide reaction products of polyepoxide compounds, polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule. And polythiols composed of thioglycolic acid, β-mercaptopropionic acid, or an esterified compound with β-mercaptobutanoic acid, and these can be used alone or in combination of two or more. ..

The content of the polythiol compound is the total of acryloyl morpholine and the urethane (meth) acrylate compound (A) having a polycarbonate structure (when the following ethylenically unsaturated compound (C) is contained, the total is further (C). ) It is preferably 0.01 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight, based on 100 parts by weight.

Further, in the active energy ray-curable adhesive composition of the present invention, a solvent may be used to adjust the viscosity at the time of coating, if necessary, but the solvent may remain in the adhesive layer or the solvent may remain. Since the curing component may volatilize when the solvent dries, it is preferable to use it as a solvent-free adhesive composition that does not substantially contain a solvent.
The term "substantially free of solvent" means that the content of the solvent is usually 1% by weight or less, preferably 0.5% by weight or less, particularly preferably 0, based on the entire active energy ray-curable adhesive composition. It means that it is 1% by weight or less.

The viscosity of the active energy ray-curable adhesive composition of the present invention at 20 ° C. is preferably 15 to 50,000 mPa · s, particularly preferably 50 to 20,000 mPa · s, from the viewpoint of coatability and the like. s, more preferably 100 to 10,000 mPa · s. If the viscosity is too low, the coatability tends to decrease, and if it is too high, the handling tends to be difficult or the coatability tends to decrease.
The viscosity is the viscosity measured using an E-type viscometer.

The active energy ray-curable adhesive composition of the present invention preferably has a metal content concentration of 50 ppm or less, particularly preferably 40 ppm or less, and further preferably 20 ppm or less. If the content is too high, the cured product (adhesive layer) tends to turn yellow.
The lower limit of the metal content concentration is usually 1 ppm.

As the metal content concentration, it is preferable that the content concentration of the metal classified into the 3rd cycle element and the 4th cycle element in the periodic table is low, and the alkali metal and the alkali classified into the 3rd cycle element and the 4th cycle element. It is particularly preferable that the contents of the earth metal and the transition metal are low, and it is further preferable that the contents of aluminum, iron, sodium and titanium are low.

If the concentration of the metal is too high, yellowing of the obtained active energy ray-curable adhesive composition and the cured product (adhesive layer) tends to occur easily. Yellowing can be determined, for example, by measuring the Hazen color number (APHA) of the active energy ray-curable adhesive composition when left for one month under a test condition of 60 ° C. APHA is preferably 300 or less, particularly preferably 200 or less, and even more preferably 100 or less.
The metal content concentration is a value measured by an ICP-AES analysis method.

Thus, the active energy ray-curable adhesive composition for polycarbonate-based members of the present invention can be obtained.
The active energy ray-curable adhesive composition of the present invention is applied onto various substrates, dried when it contains a solvent, and then an adherend is attached to the coated surface and irradiated with active energy rays. It is cured.

The active energy ray-curable adhesive composition of the present invention is particularly useful as an active energy ray-curable adhesive composition for a polycarbonate-based member because it has excellent adhesiveness to a polycarbonate-based resin. At this time, the active energy ray-curable adhesive composition is used. The base material to which the curable adhesive composition is applied may be a polycarbonate-based member, or the adherend to be adhered to the adhesive layer provided on the base material may be a polycarbonate-based member. ..

The base material to which the active energy ray-curable adhesive composition of the present invention is applied includes a (meth) acrylic resin, a polyolefin resin, a polyester resin, a polycarbonate resin, and an acrylonitrile butadiene styrene copolymer (acrylonitrile butadiene styrene copolymer). ABS), polystyrene resin, polyamide resin, etc. and their molded products (film, sheet, cup, etc.), metal base material (metal vapor deposition layer, metal plate (copper, stainless steel (SUS304, SUSBA, etc.)), aluminum, zinc , Magnesium, etc.)), glass, etc., or a composite base material thereof.
It is preferable that the base material is a molded product (polycarbonate-based member) of the polycarbonate-based resin from the viewpoint of exerting the effect of the present invention of being excellent in adhesiveness to the polycarbonate-based resin.

Examples of the adherend include articles having various metal surfaces; polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate / isophthalate copolymers; polyolefins such as polyethylene, polypropylene, and polymethylpentene. Systems Resins: Polyfluoroethylene Resins such as Polyvinyl Fluoride, Vinylidene Polyfluoride, Polyethylene Polyfluoride; Polyethylenes such as Nylon 6, Nylon 6, 6; Polyvinyl Chloride, Polyvinyl Chloride / Vinyl Acetate Copolymer, Ethylene-Vinyl Acetate Copolymers, ethylene-vinyl alcohol copolymers, vinyl polymers such as polyvinyl alcohol and vinylon; cellulose-based resins such as cellulose triacetate and cellophane; methyl polymethacrylate, ethyl polymethacrylate, ethyl polyacrylate, polyacrylic Acrylic resins such as butyl acid acid; synthetic resins such as polystyrene, polycarbonate, polyarylate, and polyimide, and molded products thereof (plates, films, sheets, cups, etc.) can be mentioned.
The adherend is preferably a molded product (polycarbonate-based member) of the polycarbonate-based resin from the viewpoint of exerting the effect of the present invention of being excellent in adhesiveness to the polycarbonate-based resin.

The method for applying the active energy ray-curable adhesive composition is not particularly limited, and for example, spray, shower, dipping, roll, spin, curtain, flow, slit, die, gravure, comma, dispenser, etc. Wet coating methods such as screen printing, inkjet printing and the like.

As such active energy rays, in addition to far-ultraviolet rays, ultraviolet rays, near-ultraviolet rays, rays such as infrared rays, electromagnetic waves such as X-rays and γ-rays, electron beams, proton beams, neutron rays and the like can be used. Curing by ultraviolet irradiation is advantageous because of its availability and price. When electron beam irradiation is performed, it can be cured without using the photopolymerization initiator (B).

As a method of curing by ultraviolet irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a non-electrode discharge lamp, an LED, etc. that emit light in the wavelength range of 150 to 450 nm are used. It suffices to irradiate about 30 to 3,000 mJ / cm ^2.
After the irradiation with ultraviolet rays, heating can be performed as necessary to complete the curing.

The thickness of the adhesive layer after curing is usually preferably 1 to 200 μm, particularly preferably 2 to 100 μm, and even more preferably 3 to 50 μm.

The active energy ray-curable adhesive composition of the present invention is particularly excellent in adhesiveness to a polycarbonate-based resin, and is also excellent in coatability and hardness of the adhesive layer after curing in a well-balanced manner. It is useful as an adhesive component for a polycarbonate-based member that adheres a member made of (polycarbonate film or the like) to another member. It is also useful as an adhesive component for various resin members other than polycarbonate-based members.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In the example, "part" and "%" mean a weight standard.
Further, the metal content concentration in the following examples is a value obtained by measuring the content concentrations of alkali metals, alkaline earth metals, and transition metals contained in the 3rd period element and the 4th period element by the ICP-AES analysis method. be.

<Example 1>
123.0 g (0.63 mol) of hydrogenated xylylene diisocyanate, polycarbonate diol (linear structure; hydroxyl value 145 mgKOH / g; Number average molecular weight 774 calculated from hydroxyl value; metal content concentration: 82 ppm) 326.8 g (0.42 mol), acryloylmorpholine 214.3 g, methoxyphenol 0.4 g as a polymerization inhibitor, dibutyltin dilaurate 0 as a reaction catalyst. 02 g was charged and reacted at 60 ° C. When the residual isocyanate group became 2.7% or less, 50.3 g (0.43 mol) of 2-hydroxyethyl acrylate was further charged and reacted at 60 ° C., and the residual isocyanate group became 0.3% or less. At that point, the reaction was terminated, and 285.7 g of acryloyl morpholine was further charged, and a urethane (meth) acrylate compound (A-1) having a carbonate structure (weight average molecular weight: 12,000) and acryloyl morpholine (weight ratio 50:) were added. A mixture of 50) was obtained.
An α-hydroxyalkylphenone-based photopolymerization initiator (BASF, “Irgacure 184”) was added as a photopolymerization initiator (B) to 100 parts of the obtained mixture of urethane (meth) acrylate-based compound and acryloyl morpholine. Four parts were blended to obtain an active energy ray-curable adhesive composition (20 ° C. viscosity: 11,000 mPa · s).

<Example 2>
In a four-necked flask equipped with a thermometer, agitator, a water-cooled condenser, and a nitrogen gas inlet, 73.8 g (0.38 mol) of hydrogenated xylylene diisocyanate, polycarbonate diol (linear structure; hydroxyl value 145 mgKOH / g; Number average molecular weight 774 calculated from hydroxyl value; metal content concentration: 82 ppm) 196.1 g (0.25 mol), acryloylmorpholin 128.6 g, methoxyphenol 0.4 g as a polymerization inhibitor, dibutyltin dilaurate 0. 02 g was charged and reacted at 60 ° C. When the residual isocyanate group became 2.7% or less, 30.2 g (0.26 mol) of 2-hydroxyethyl acrylate was further charged and reacted at 60 ° C., and the residual isocyanate group became 0.3% or less. At that point, the reaction was terminated, and 571.4 g of acryloyl morpholine was further charged, and urethane (meth) acrylate compound (A-1) having a carbonate structure (weight average molecular weight: 12,000) and acryloyl morpholine (weight ratio 30:) were added. A mixture of 70) was obtained.
An α-hydroxyalkylphenone-based photopolymerization initiator (BASF, “Irgacure 184”) was added as a photopolymerization initiator (B) to 100 parts of the obtained mixture of urethane (meth) acrylate-based compound and acryloylmorpholine. Four parts were blended to obtain an active energy ray-curable adhesive composition (20 ° C. viscosity: 700 mPa · s).

<Example 3>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 24.6 g (0.13 mol) of hydrogenated xylylene diisocyanate, a polycarbonate diol (linear structure; hydroxyl value 145 mgKOH / g; Number average molecular weight calculated from hydroxyl value 774; Metal content concentration: 82 ppm) 65.4 g (0.08 mol), acryloylmorpholine 42.9 g, methoxyphenol 0.4 g as a polymerization inhibitor, dibutyltin dilaurate 0. 02 g was charged and reacted at 60 ° C. When the residual isocyanate group became 2.7% or less, 10.1 g (0.09 mol) of 2-hydroxyethyl acrylate was further charged and reacted at 60 ° C., and the residual isocyanate group became 0.3% or less. At that point, the reaction was terminated, and 857.1 g of acryloyl morpholine was further charged, and urethane (meth) acrylate compound (A-1) having a carbonate structure (weight average molecular weight: 12,000) and acryloyl morpholine (weight ratio 10:) were added. A mixture of 90) was obtained.
To 100 parts of the obtained mixture of urethane (meth) acrylate compound and acryloylmorpholin, 4 parts of α-hydroxyalkylphenone-based photopolymerization initiator (BASF, "Irgacure 184") was blended as a photopolymerization initiator. Then, an active energy ray-curable adhesive composition (20 ° C. viscosity: 50 mPa · s) was obtained.

<Example 4>
In a four-port flask equipped with a thermometer, agitator, a water-cooled condenser, and a nitrogen gas inlet, 103.6 g (0.53 mol) of hydrogenated xylylene diisocyanate, polycarbonate diol (linear structure; hydroxyl value 225 mgKOH / g; Number average molecular weight calculated from hydroxyl value 499; Metal content: 13 ppm) 133.0 g (0.27 mol), acryloylmorpholin 128.6 g, dibutylhydroxytoluene 0.4 g as a polymerization inhibitor, dibutyltin dilaurate 0 as a reaction catalyst 0.02 g was charged and reacted at 60 ° C. When the residual isocyanate group became 6.1% or less, 63.5 g (0.55 mol) of 2-hydroxyethyl acrylate was further charged and reacted at 60 ° C., and the residual isocyanate group became 0.3% or less. At that point, the reaction was terminated, and 571.4 g of acryloyl morpholine was further charged, and urethane (meth) acrylate compound (A-2) having a carbonate structure (weight average molecular weight: 5,000) and acryloyl morpholine (weight ratio 30) were added. : 70) mixture was obtained.
An α-hydroxyalkylphenone-based photopolymerization initiator (BASF, “Irgacure 184”) was added as a photopolymerization initiator (B) to 100 parts of the obtained mixture of urethane (meth) acrylate-based compound and acryloylmorpholine. Four parts were blended to obtain an active energy ray-curable adhesive composition (20 ° C. viscosity: 330 mPa · s).

<Example 5>
Hydrogenated xylylene diisocyanate 69.2 g (0.36 mol), polycarbonate diol (linear structure; hydroxyl value 106 mgKOH / g; Number average molecular weight calculated from hydroxyl value 1059) 188.5 g (0.18 mol), 128.6 g of acryloyl morpholine, 0.4 g of dibutylhydroxytoluene as a polymerization inhibitor, 0.02 g of dibutyltin dilaurate as a reaction catalyst, 60 The reaction was carried out at ° C. When the residual isocyanate group became 3.9% or less, 42.4 g (0.36 mol) of 2-hydroxyethyl acrylate was further charged and reacted at 60 ° C., and the residual isocyanate group became 0.3% or less. At that point, the reaction was terminated, and 571.4 g of acryloyl morpholine was further charged, and urethane (meth) acrylate compound (A-3) having a carbonate structure (weight average molecular weight: 8,400) and acryloyl morpholine (weight ratio 30) were added. : 70) mixture was obtained.
An α-hydroxyalkylphenone-based photopolymerization initiator (BASF, “Irgacure 184”) was added as a photopolymerization initiator (B) to 100 parts of the obtained mixture of urethane (meth) acrylate-based compound and acryloylmorpholine. Four parts were blended to obtain an active energy ray-curable adhesive composition (20 ° C. viscosity: 420 mPa · s).

<Example 6>
In a four-necked flask equipped with a thermometer, agitator, a water-cooled condenser, and a nitrogen gas inlet, 59.5 g (0.31 mol) of hydrogenated xylylene diisocyanate, polycarbonate diol (linear structure; hydroxyl value 106 mgKOH / g; Number average molecular weight calculated from hydroxyl value 1059) 216.2 g (0.20 mol), acryloyl morpholine 128.6 g, dibutyl hydroxytoluene 0.4 g as a polymerization inhibitor, dibutyl tin dilaurate 0.02 g as a reaction catalyst, 60 The reaction was carried out at ° C. When the residual isocyanate group became 2.1% or less, 24.3 g (0.21 mol) of 2-hydroxyethyl acrylate was further charged and reacted at 60 ° C., and the residual isocyanate group became 0.3% or less. At that point, the reaction was terminated, and 571.4 g of acryloyl morpholine was further charged, and urethane (meth) acrylate compound (A-4) having a carbonate structure (weight average molecular weight: 14,000) and acryloyl morpholine (weight ratio 30) were added. : 70) mixture was obtained.
An α-hydroxyalkylphenone-based photopolymerization initiator (BASF, “Irgacure 184”) was added as a photopolymerization initiator (B) to 100 parts of the obtained mixture of urethane (meth) acrylate-based compound and acryloylmorpholine. Four parts were blended to obtain an active energy ray-curable adhesive composition (20 ° C. viscosity: 870 mPa · s).

<Comparative example 1>
172.4 g (0.89 mol) of hydrogenated xylylene diisocyanate, polycarbonate diol (linear structure; hydroxyl value 145 mgKOH / g; Number average molecular weight 774 calculated from hydroxyl value; metal content: 82 ppm) 457.9 g (0.59 mol), ethyl acetate 300.0 g, methoxyphenol 0.4 g as a polymerization inhibitor, dibutyltin dilaurate 0. 02 g was charged and reacted at 60 ° C. When the residual isocyanate group became 2.7% or less, 69.7 g (0.60 mol) of 2-hydroxyethyl acrylate was further charged and reacted at 60 ° C., and the residual isocyanate group became 0.3% or less. At that time, the reaction was terminated to obtain an ethyl acetate solution of a urethane (meth) acrylate compound (A-1) having a carbonate structure (weight average molecular weight: 11,000).
An α-hydroxyalkylphenone-based photopolymerization initiator (BASF, “Irgacure 184”) was added as a photopolymerization initiator (B) to 100 parts of the obtained mixture of urethane (meth) acrylate-based compound and ethyl acetate. 2.8 parts were blended to obtain an active energy ray-curable adhesive composition (20 ° C. viscosity: 3,000 mPa · s).

<Comparative example 2>
4 parts of α-hydroxyalkylphenone-based photopolymerization initiator (BASF, “Irgacure 184”) is blended with 100 parts of acryloyl morpholine as a photopolymerization initiator (B) to form an active energy ray-curable adhesive. A product (20 ° C. viscosity: 12 mPa · s) was obtained.

<Comparative example 3>
162.3 g (0.84 mol) of hydrogenated xylylene diisocyanate, polyester diol (hydroxyl value 63.4 mgKOH / g; hydroxyl value) in a four-necked flask equipped with a thermometer, agitator, water-cooled condenser, and nitrogen gas inlet. 739.3 g (0.42 mol) of molecular weight calculated from 1770) and 0.02 g of dibutyltin dilaurate as a reaction catalyst were charged and reacted at 60 ° C. When the residual isocyanate group became 3.9% or less, 98.4 g (0.85 mol) of 2-hydroxyethyl acrylate and 0.4 g of methoxyphenol as a polymerization inhibitor were further charged and reacted at 60 ° C. to remain. The reaction was terminated when the isocyanate group content was 0.3% or less to obtain a urethane (meth) acrylate-based compound (A'-1) (weight average molecular weight: 10,000) containing no carbonate structure.
70 parts of acryloyl morpholine was added to 30 parts of the obtained urethane (meth) acrylate compound, and an α-hydroxyalkylphenone-based photopolymerization initiator (BASF, “Irgacure 184”) was used as the photopolymerization initiator (B). Four parts were blended to obtain an active energy ray-curable adhesive composition (20 ° C. viscosity: 420 mPa · s).

<Comparative example 4>
Hydrogenated diphenylmethane diisocyanate 366.3 g (1.40 mol), polytetramethylene ether glycol (hydroxyl value 167 mgKOH / g; hydroxyl value) in a four-necked flask equipped with a thermometer, agitator, water-cooled condenser, and nitrogen gas inlet. The number average molecular weight calculated from 672; metal content: 4 ppm) 469.1 g (0.70 mol), and 0.02 g of dibutyltin dilaurate as a reaction catalyst were charged and reacted at 60 ° C. When the residual isocyanate group was 7.0% or less, 164.6 g (1.42 mol) of 2-hydroxyethyl acrylate and 0.4 g of methoxyphenol as a polymerization inhibitor were further charged and reacted at 60 ° C. to remain. The reaction was terminated when the isocyanate group content was 0.3% or less to obtain a urethane (meth) acrylate-based compound (A'-2) (weight average molecular weight: 5,000) containing no carbonate structure.
70 parts of acryloyl morpholine and 4 parts of α-hydroxyalkylphenone-based photopolymerization initiator (BASF, “Irgacure 184”) are blended with 30 parts of the obtained urethane (meth) acrylate compound. Then, an active energy ray-curable adhesive composition (20 ° C. viscosity: 310 mPa · s) was obtained.

<Comparative example 5>
An active energy ray-curable adhesive composition (20 ° C. viscosity: 150 mPa · s) was obtained in the same manner as in Example 2 except that the acryloyl morpholine used in Example 2 was changed to tetrahydrofurfuryl acrylate.

<Comparative Example 6>
An active energy ray-curable adhesive composition (20 ° C. viscosity: 960 mPa · s) was obtained in the same manner as in Example 2 except that the acryloyl morpholine used in Example 2 was changed to cyclic trimethylolpropane formal acrylate. ..

<Comparative Example 7>
An active energy ray-curable adhesive composition (20 ° C. viscosity: 1,400 mPa · s) was obtained in the same manner as in Example 2 except that the acryloyl morpholine used in Example 2 was changed to isobornyl acrylate. ..

<Comparative Example 8>
An active energy ray-curable adhesive composition (20 ° C. viscosity: 40 mPa · s) was obtained in the same manner as in Example 2 except that the acryloyl morpholine used in Example 2 was changed to dimethylacrylamide.

<Comparative Example 9>
The active energy ray-curable adhesive composition (20 ° C. viscosity: 9,100 mPa · s) was the same as in Example 2 except that the acryloyl morpholine used in Example 2 was changed to tricyclodecanedimethanol diacrylate. Got

The active energy ray-curable adhesive compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 9 were evaluated as follows. The results are shown in Table 1.

[Preparation of evaluation sample]
After drying the active energy ray-curable adhesive composition on a PET film (easy-adhesive polyethylene terephthalate (PET) film (manufactured by Toyobo; Cosmo Shine A4300, thickness 125 μm) provided with an easy-adhesive layer) using a bar coater. An adhesive layer was formed by coating so that the film thickness was 5 μm (only Comparative Example 1 containing a solvent was dried at 60 ° C. for 3 minutes after coating) to form an adhesive layer. At this time, an adhesive test was performed. A surface not coated with the adhesive composition was provided on the edge of the PET film so that the film could be peeled off.
After that, it was attached to the obtained adhesive layer on a polycarbonate standard test plate (manufactured by Nippon Test Panel Co., Ltd.), and from the PET film side, using a high-pressure mercury lamp 80W and one lamp, from a height of 18 cm to 2.6 m / min. Two-pass ultraviolet irradiation (cumulative irradiation amount 1,000 mJ / cm ² ) was performed at the same conveyor speed to cure the active energy ray-curable adhesive composition to form an adhesive layer, and an evaluation sample was prepared.

[Appropriate coating]
The coating suitability when the adhesive layer was formed was evaluated based on the viscosity range of the active energy ray-curable adhesive composition as described below.
◎ ・ ・ ・ 100 to 10,000 mPa ・ s
○ ・ ・ ・ 50 to less than 100 mPa ・ s or more than 10,000 to 20,000 mPa ・ s
Δ ・ ・ ・ 15 to less than 50 mPa ・ s, or more than 20,000 to 50,000 mPa ・ s
× ・ ・ ・ Less than 15 mPa · s or more than 50,000 mPa · s

〔Adhesiveness〕
The end of the PET film that was not adhered to the polycarbonate plate of the evaluation sample prepared above was fixed with a chuck, and the adhesiveness was evaluated by a 90 ° peel test by Shimadzu Autograph AG-X (Shimadzu Corporation). The width of the PET substrate in the test was 20 mm, and the measurement was performed at a peel speed of 300 mm / min.
(Evaluation criteria)
◯: The PET base material was torn (material rupture) due to the strong adhesive force, and there was no change in the adhesive layer.
Δ: The average adhesive strength was 2.0 N / 20 mm or more, but the PET base material was not destroyed.
X ... The average adhesive strength was less than 2.0 N / 20 mm.

〔Pencil hardness〕
The active energy ray-curable adhesive composition is coated on a PET film provided with an easy-adhesion layer using a bar coater so that the film thickness after drying is 5 μm, and when a solvent is contained. It was dried at 60 ° C. for 3 minutes. After that, using a high-pressure mercury lamp 80W and one lamp, 2-pass ultraviolet irradiation (integrated irradiation amount 1,000 mJ / cm ² ) was performed from a height of 18 cm at a conveyor speed of 2.6 m / min to obtain a cured coating film. Formed. The hardness of the obtained cured coating film was measured according to JIS K 5600-5-4.
(Evaluation criteria)
○ ・ ・ ・ HB or higher △ ・ ・ ・ B
× ・ ・ ・ 2B or less

〔Heat-resistant〕
For the active energy ray-curable adhesive composition, the Hazen color number (APHA) was measured using a spectral color difference meter "SE6000: manufactured by Nippon Denshoku Industries Co., Ltd.". Further, the active energy ray-curable adhesive composition was placed in a closed glass test container and stored under heat resistance conditions: 60 ° C. for 8 weeks, and the APHA value after the heat resistance test was measured.
As a result, in Examples 4 to 6 using the polycarbonate polyol having a metal content of 14 ppm, the increase in APHA was suppressed to 100 or less before and after the heat resistance test, and the yellowing was less.

From the above evaluation results, the active energy ray-curable adhesive compositions of Examples 1 to 6 are excellent in coating suitability, excellent adhesion to polycarbonate-based members, and excellent hardness of the cured adhesive layer. Met.
On the other hand, in Comparative Example 1 containing no acryloyl morpholine, although the coating suitability was satisfied, the hardness of the adhesive layer was very low, and the adhesiveness was also insufficient. Further, Comparative Example 2 containing no urethane (meth) acrylate compound is inferior in coating suitability, and Comparative Examples 3 and 4 using a urethane methacrylate compound having no carbonate structure are after curing. The hardness of the adhesive layer was low, which was not satisfactory. Further, Comparative Examples 5 to 9 containing no acryloyl morpholine and using other active energy ray-curable monomers were inferior in adhesiveness or hardness of the adhesive layer.

Since the active energy ray-curable adhesive composition for a polycarbonate-based member of the present invention is particularly excellent in adhesiveness to a polycarbonate-based resin, an adhesive component between a member made of a polycarbonate-based resin (polycarbonate film or the like) and another member. It is very useful as an adhesive between a liquid crystal display and a carbonate-based resin base material because it is excellent in coatability, curability, hardness, transparency, and heat resistance.

Claims (7)

Contains acryloyl morpholine and a urethane (meth) acrylate compound (A) having a carbonate structure,
The weight average molecular weight of the urethane (meth) acrylate compound (A) is 5000 to 14000 .
The content ratio (weight ratio) of the acryloyl morpholine and the urethane (meth) acrylate compound (A) having a carbonate structure is acryloyl morpholine: urethane (meth) acrylate compound (A) = 90: 10 to 50:50. An active energy ray-curable adhesive composition for a polycarbonate-based member. The urethane (meth) acrylate-based compound (A) is a reaction product of a polyhydric isocyanate-based compound (a1), a hydroxyl group-containing (meth) acrylate-based compound (a2), and a polycarbonate-based polyol compound (a3). The active energy ray-curable adhesive composition for a polycarbonate-based member according to claim 1. The active energy ray-curable adhesive composition for a polycarbonate-based member according to claim 2, wherein the polycarbonate-based polyol compound (a3) has a metal-containing concentration of 100 ppm or less. The active energy ray-curable adhesive composition for a polycarbonate-based member according to claim 3, wherein the metal content is the concentration of the metal contained in the 3rd period element and the 4th period element. The active energy for a polycarbonate-based member according to claim 3 or 4, wherein the metal content is the concentration of an alkali metal, an alkaline earth metal, or a transition metal contained in the 3rd period element and the 4th period element. Linear curable adhesive composition. The active energy ray-curable adhesive composition for a polycarbonate-based member according to any one of claims 1 to 5, further comprising a photopolymerization initiator (B). An adhesive for a polycarbonate-based member, which comprises using the active energy ray-curable adhesive composition according to any one of claims 1 to 6.