TWI674277B - (meth) acryloyloxy group-containing polymer - Google Patents

Abstract

An object of the present invention is to provide a (meth) acryloxy group-containing polymer which can accelerate the hardening speed of a composition. The (meth) acryloxy group-containing polymer according to the present invention, wherein the backbone of the (meth) acryloxy group has a monomer composed of at least one monomer selected from the group consisting of butadiene and isoprene. A polymer or a hydride thereof, and having a functional group represented by the following formula (1) at least one terminal (wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and m and n each independently represent 1 to 5 , * Indicates the (meth) acrylic fluorenyl group-containing polymer of the bonding position with the aforementioned main chain).

Description

(Meth) acrylic acid-containing polymer

The present invention relates to a polymer containing (meth) acrylic acid.

In recent years, a composition containing a photopolymerizable resin is known as an adhesive or an adhesive for electronic materials.

For example, Patent Document 1 describes a composition for a photocurable transparent adhesive film (claim 1), which contains (A) a polyolefin having a (meth) acrylfluorene group having a weight average molecular weight of 10,000 to 300,000. A compound, (B) a (meth) acrylate having a hydroxyl group, (C) a photopolymerizable monomer other than the (meth) acrylate having a hydroxyl group, and (D) a photopolymerization initiator, wherein (A) The (meth) acrylfluorene-containing polyolefin having a weight average molecular weight of 10,000 to 300,000 is obtained by reacting a polyolefin polyol with a polyfunctional isocyanate compound, and then reacting the remaining hydroxyl or isocyanate groups with 50 to 80 mol% of the compound having a (meth) acrylfluorenyl group reacts, so that the (meth) acrylic acid urethane compound obtained by introducing the (meth) acrylfluorenyl group into the molecule is Light other than hydroxyl (meth) acrylate The total amount of the polymerizable monomers is 0.1% by mass or less of the carboxyl group-containing monomer contained in the photopolymerizable monomer other than the (C) acrylate having a hydroxyl group. In addition, Example 2 of Patent Document 1 describes a composition containing a reaction of 1 mole of isophorone diisocyanate and 2 moles of hydrogenated terminal hydroxy polybutadiene, and the residual isocyanate group is 0.1%. In the following, the (meth) acrylfluorenyl-containing polyolefin compound (A-2), hydroxyethyl acrylate, cyclohexyl acrylate, and a photopolymerization initiator obtained after the reaction of 1.4 mol of 2-isocyanate ethyl acrylate Wait.

[Prior technical literature] [Patent Literature]

[Patent Document 1] International Publication No. 2012/043550

Among them, the present inventors have known that when a composition containing a (meth) acrylfluorene-containing polyolefin compound is prepared in accordance with Patent Document 1, the hardening speed of such a composition may be slowed down.

Therefore, an object of the present invention is to provide a (meth) acrylic fluorenyl group-containing polymer which can accelerate the hardening speed of a composition.

The present inventors have intensively studied in order to solve the above problems, and found that the backbone as a backbone has a polymer or a hydride formed of at least one monomer selected from the group consisting of butadiene and isoprene. , In addition, a (meth) acrylic acid group-containing polymer having a specific functional group having two (meth) acrylic acid groups at the terminal can accelerate the hardening speed of the composition and complete the present invention.

That is, the present inventors have found that the above problems can be solved by the following configuration.

A (meth) acryloxy group-containing polymer, wherein a backbone of the polymer includes at least one monomer selected from the group consisting of butadiene and isoprene. A polymer or a hydride thereof, and having a functional group represented by the following formula (1) at the terminal,

In formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, m and n each independently represent 1 to 5, and * represents a bonding position with the aforementioned main chain.

2. The (meth) acryloxy group-containing polymer according to claim 1, wherein the main chain and the functional group are bonded directly or through a hetero atom or an organic group.

3. The (meth) acrylic fluorenyl group-containing polymer according to claim 2, wherein the organic group has two or more urethane bonds.

4. The (meth) acrylic fluorenyl group-containing polymer according to any one of claims 1 to 3, wherein the aforementioned skeleton has a structure selected from the group consisting of repeating units represented by the following formulae (Ia) to (Ic) At least one of the group,

In the formulae (Ia) to (Ic), the double line of the dashed line and the solid line represents a single bond or a double bond.

5. The (meth) acrylic fluorenyl group-containing polymer according to claim 4, wherein the total of the repeating units represented by the aforementioned formulae (Ia) to (Ic) is represented by the aforementioned formula (Ia) The content of the repeating unit 1 is 0 ~ 40 mole%, With respect to the total of the repeating units represented by the aforementioned formulae (Ia) to (Ic), the content 2 of the repeating units represented by the aforementioned formula (Ib) is 0 to 100 mole%, The content of the repeating unit 3 represented by the aforementioned formula (Ic) is 0 to 100 mol% relative to the total of the repeating units represented by the aforementioned formulas (Ia) to (Ic).

6. The (meth) propenyloxy group-containing polymer according to any one of claims 1 to 5, which has 3 or more (meth) propenyloxy groups in one molecule.

According to the present invention, it is possible to provide a (meth) acryloxy group-containing polymer which can accelerate the hardening speed of a composition.

Hereinafter, the present invention will be described in detail.

In addition, in this specification, (meth) acrylate means an acrylate or a methacrylate, (meth) acrylic 醯 means acryl 醯 or methacryl 醯, and (meth) acrylic acid means acrylic acid or methacrylic acid.

In addition, the numerical range indicated by "~" in this specification means the range in which the numerical value described before and after "~" is included as a lower limit and an upper limit.

In addition, in this specification, when a component contains two or more substances, the content of the said component means the total content of two or more substances.

[Polymer with (meth) acrylic acid]

In the (meth) acryloxy group-containing polymer (polymer of the present invention) of the present invention, the backbone as a main chain has at least 1 selected from the group consisting of butadiene and isoprene. (Meth) acryloxy group-containing polymer having a functional group represented by the following formula (1) at the end,

In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, m and n each independently represent 1 to 5, and * represents a bonding position with the aforementioned main chain.

Since the polymer of the present invention has such a structure, it is considered that it can obtain a desired effect. Although the reason is not clear, it can be roughly estimated as follows.

That is, it is presumed that the functional group located at the terminal of the polymer of the present invention has two (meth) acrylic fluorenyloxy groups, and is therefore more reactive than the polymer having one (meth) acryl fluorenyloxy group at the terminal It hardens quickly.

In addition, it is presumed that the composition having the polymer of the present invention is excellent in adhesion strength (especially adhesion strength under high temperature and high humidity conditions) due to such high reactivity.

Hereinafter, the polymer of the present invention will be described in detail.

<Main chain>

The polymer of the present invention has, as a backbone of the main chain thereof, a polymer or a hydride formed of the polymer including at least one monomer selected from the group consisting of butadiene and isoprene.

The main chain may be any of a homopolymer and a copolymer. When the main chain is a copolymer, examples of the copolymer include random copolymers, block copolymers, graft copolymers, and combinations thereof. As a polymer, for example Examples include polybutadiene, polyisoprene, and butadiene isoprene copolymer.

In addition, the main chain may be a hydride of a polymer formed from the monomers. The hydride may be one in which some or all of the double bonds possessed by the polymer are hydrogenated. The hydrogenation rate of the polymer is not particularly limited.

The skeleton of the main chain of the polymer of the present invention preferably has at least one selected from the group consisting of repeating units represented by the following formulae (Ia) to (Ic),

(In the formulae (Ia) to (Ic), the double line of the dashed line and the solid line represents a single bond or a double bond.)

The content of the repeating unit 1 represented by the formula (Ia) 1 is preferably 0 to 40 mole%, and more preferably 0 to the total of the repeating units represented by the formulae (Ia) to (Ic). 35 mole%.

The content of the repeating unit 2 represented by the above formula (Ib) is preferably 0 to 100 mole%, and more preferably 0 to the total of the repeating units represented by the above formulas (Ia) to (Ic). 90 mol%.

The content 3 of the repeating unit represented by the above formula (Ic) is preferably relative to the total of the repeating units represented by the above formulas (Ia) to (Ic). 0 to 100 mole%, more preferably 0 to 50 mole%.

As a combination of the repeating units represented by the formula (Ia) to the formula (Ic), for example, a combination of the repeating units represented by the formula (1a) and the formula (1b) can be cited as one of the preferable aspects.

In addition, when the backbone of the main chain of the polymer of the present invention has at least one selected from the group consisting of repeating units represented by formula (Ia) to formula (Ic), the content of 1-3 may not be all. Also 0.

In addition, the respective ratios of the repeating units represented by the formula (Ia) to the formula (Ic) in the base polymer used in the production of the polymer of the present invention can be reflected to the above-mentioned contents 1, 2, and 3.

The above contents 1, 2 and 3 can be calculated from the results of ¹ H-NMR (nuclear magnetic resonance) and ¹³ C-NMR analysis.

<Functional group>

The polymer of the present invention has a functional group represented by the following formula (1) at its terminal.

In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, m and n each independently represent 1 to 5, and * represents a bonding position with the aforementioned main chain.

In formula (1), m is preferably 1 to 3.

N is preferably 1 to 3.

R ¹ and R ² may be the same or different.

Examples of the functional group represented by the formula (1) include a functional group represented by the following formula (1 ').

In the formula (1 ′), R ¹¹ , R ¹² , m1, n1, and * are the same as R ¹ , R ² , m, n, and * in the formula (1), respectively.

Furthermore, the oxygen atom adjacent to * in the formula (1 ′) may form a part of a bond having an oxygen atom (for example, a urethane bond). The bond having an oxygen atom may be included in the organic group described below.

The polymer of the present invention has one or more functional groups represented by formula (1) in one molecule. The number of the functional groups may be 10 or less. The number of the functional groups is preferably one or two.

The polymer of the present invention may have a functional group represented by formula (1) at at least one terminal or at all terminals. When the main chain is linear, one or both ends of the main chain may have a functional group represented by formula (1).

In the polymer of the present invention, the main chain and the functional group may be bonded directly or through a hetero atom or an organic group.

(Heteroatom)

The hetero atom may be at least divalent. Examples of the divalent hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.

(Organic)

The organic group which bonds the said main chain and the said functional group is not specifically limited. For example, a hydrocarbon group which may have a hetero atom is mentioned. The organic group may be divalent or more.

Examples of the hydrocarbon group include an aliphatic hydrocarbon group (including an alicyclic type), an aromatic hydrocarbon group, and a combination thereof. The hydrocarbon group may be any of linear, branched, and cyclic. The hydrocarbyl group may have an unsaturated bond.

Examples of the hydrocarbon group include residues of alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, and hexamethylene; residues of alicyclic hydrocarbon groups such as cyclohexane: residues of aromatic hydrocarbon groups such as benzene ; Residue derived from a combination of an alkyl group of an isophorone diisocyanate and an alicyclic hydrocarbon group.

Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen, and a combination thereof.

Examples of the hetero atom-containing substituent include a urethane bond, an ester bond, and a urea bond. Among these, as one of the preferable aspects, a urethane bond is mentioned.

The number of the above-mentioned substituents having one organic group may be one or two or more. As one of the preferred embodiments, the number may be two.

When the number of the above-mentioned substituents which one organic group has is 2, a hydrocarbon group which may have a hetero atom may be arranged between the two substituents. this In this case, the organic group can be represented by the following formula (6), for example.

Formula (6): Hydrocarbyl-substituent ⁶² -which may have -substituent ⁶¹ -heteroatom

In the formula (6), the substituent ⁶¹ and the substituent ⁶² may be the same or different, and are a substituent in which the above hetero atom is combined.

In addition, "-" in Formula (6) represents a bond (the same applies hereinafter).

The number of (meth) acrylic fluorenyloxy groups contained in one molecule of the polymer of the present invention is preferably two or more, more preferably three to six, and particularly preferably four. Among them, at least two (meth) acrylfluorenyl groups are derived from the functional group represented by the above formula (1).

The polymer of the present invention may further have a group having a (meth) acrylfluorenyl group (hereinafter sometimes referred to as "other group") different from the functional group described above.

The bonding position of the other groups is not particularly limited, but examples include the terminal of the polymer of the present invention.

Examples of the other groups include a group represented by the following formula (7).

Equation (7): CH ₂ = CR ⁷² -CO-OR ^71- *

In the formula (7), R ⁷² is a hydrogen atom or a methyl group, R ⁷¹ is a hydrocarbon group, and * represents a bonding position with the main chain.

Examples of the hydrocarbon group represented by R ⁷¹ include an aliphatic hydrocarbon group (including an alicyclic type), an aromatic hydrocarbon group, and a combination thereof. The hydrocarbon group may be any of linear, branched, and cyclic. The hydrocarbyl group may have an unsaturated bond. Specific examples of the hydrocarbon group include an alkylene group having 1 to 10 carbon atoms, and specific examples include a methylene group, an ethylene group, a trimethylene group, and a butenyl group.

The polymer of the present invention may have 0 or more of the above-mentioned other groups in one molecule. The number of the other bases may be 10 or less. The number of the other bases is preferably one or two.

The other (meth) acrylfluorenyl groups may be bonded to the main chain directly or through a hetero atom or an organic group. Heteroatoms and organic groups are the same as described above.

Examples of the polymer of the present invention include a polymer represented by the following formula (4).

Formula (4): [may also have functional group ⁴¹ -substituent ⁴¹ -heteroatom hydrocarbon group-substituent ⁴² ] ₂ -main chain

In the formula (4), the functional group ⁴¹ represents a functional group represented by the formula (1) or the other group, and at least one of the two functional groups ⁴¹ is a functional group represented by the formula (1). The functional group represented by formula (1), other groups, and a hydrocarbon group having a hetero atom may be the same as those described above.

In the formula (4), the substituent ⁴¹ and the substituent ^{42 are the} same as the substituent ⁶¹ and the substituent ⁶² described above.

In the formula (4), "the substituent ⁴¹ -a hydrocarbon group which may have a hetero atom-the substituent ⁴² " corresponds to an organic group.

The number average molecular weight of the polymer of the present invention is preferably 5,000 to 100,000, and more preferably 10,000 to 70,000. The number-average molecular weight of the polymer of the present invention is a value obtained by measuring with a gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene.

The polymer of the present invention can be used alone or in combination of two or more kinds.

The polymer of the present invention may be one having a photopolymerizable property as a preferable aspect.

The light for polymerizing the polymer of the present invention is not particularly limited. Examples include ultraviolet rays.

The polymer of the present invention can be polymerized by reacting a (meth) acryloxy group having a functional group represented by formula (1).

The temperature conditions at which the polymer of the present invention is polymerized are not particularly limited. For example, it can be 0 ~ 150 ° C.

(Method for producing polymer of the present invention)

As a method for producing the polymer of the present invention, for example, the following method can be enumerated: Step 1: reacting a raw polymer having an active hydrogen-containing group at the terminal and polyisocyanate to produce an isocyanate group-containing polymer having an isocyanate group at the terminal, as well as Step 2: Then, it reacts the isocyanate group-containing polymer prepared above with a (meth) acryloxy group and a (meth) acryloxy group-containing compound having an active hydrogen group, Manufacture of (meth) acrylic fluorenyl-containing polymers.

((step 1))

Step 1 is a step of reacting a base polymer having a terminal group containing an active hydrogen with a polyisocyanate to produce an isocyanate group-containing polymer having an isocyanate group at a terminal. The isocyanate group-containing polymer may have an isocyanate group at at least one terminal or all terminals.

Base polymer

Examples of the raw material polymer used in step 1 include a polymer having a backbone as a main chain and a polymer thereof including at least one monomer selected from the group consisting of butadiene and isoprene or a hydride thereof. And an active hydrogen-containing polymer having an active hydrogen-containing group (eg, a hydroxyl group) at the terminal. The active hydrogen-containing polymer may have an active hydrogen-containing group at at least one terminal or all terminals.

Examples of the skeleton of the main chain of the base polymer include those having at least one selected from the group consisting of repeating units represented by the following formulae (Ia) to (Ic).

(In the formulae (Ia) to (Ic), the double line of the dashed line and the solid line represents a single bond or a double bond.)

The content 4 of the repeating unit represented by the formula (Ia) in the base polymer is the same as the above-mentioned content 1 in the polymer of the present invention. The content 5 of formula (Ib) in the base polymer is the same as the above-mentioned content 2, and the content 6 of formula (Ic) in the base polymer is the same as the above-mentioned content 3.

Examples of the base polymer include polymers containing hydroxyl groups at both ends represented by the following formulae (a1) to (a4).

In formulas (a1) and (a2), m independently represents an integer of 15 to 90,

In formula (a3), m is an integer of 0-50. n is an integer from 0 to 90, preferably 5 to 90, and the total of m and n may be 140 or less, preferably 90 or more In the following, m and n are not 0 at the same time. In formula (a4), m is an integer from 10 to 90.

The number average molecular weight of the base polymer is preferably 1,000 to 10,000, and more preferably 1500 to 7000. The number-average molecular weight of the base polymer is a value obtained by measuring with a gel permeation chromatography (GPC) in terms of polystyrene, using tetrahydrofuran as a solvent, and converting it into polystyrene.

The base polymers can be used individually or in combination of two or more kinds.

Polyisocyanate

The polyisocyanate system used in step 1 may have two isocyanate groups in the molecule, and is not particularly limited.

Specific examples of the polyisocyanate include TDI (e.g., toluene 2,4-diisocyanate (2,4-TDI), toluene 2,6-diisocyanate (2,6-TDI)) , MDI (such as 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4- Phenyl diisocyanate, xylylene diisocyanate (XDI), tetraxylylene diisocyanate (TMXDI), benzylamine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenyl Aromatic diisocyanates such as methyl triisocyanate; hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), Cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanate methyl) cyclohexane (H ₆ XDI), dicyclohexyl methane diisocyanate (H ₁₂ MDI), etc. Aliphatic diisocyanates (including diisocyanates having alicyclic hydrocarbon groups); isocyanurate bodies, biuret bodies, adducts, and the like of the diisocyanates. Polyisocyanate may be used individually by 1 type, and may use 2 or more types together.

The amount ratio of the base polymer to the polyisocyanate may be a value (for example, 1.1 to 2) in which the molar ratio (isocyanate group / active hydrogen group-containing) of the active hydrogen group and the isocyanate group is greater than 1.

In step 1, an isocyanate group-containing polymer can be produced by mixing a base polymer with a polyisocyanate, and heating the polymer at 50 to 120 ° C. under a nitrogen environment.

Furthermore, in step 1, since a plurality of isocyanate groups having one polyisocyanate are reacted with the base polymer, the base polymer can also achieve high molecular weight.

((Step 2))

Step 2 is a step of reacting the isocyanate group-containing polymer obtained in step 1 with a (meth) propenyloxy group and a (meth) propenyloxy group-containing compound containing an active hydrogen group to produce a polymer containing Step of polymer of (meth) acrylic acid.

The (meth) propenyloxy group-containing compound used in step 2 is a compound having a (meth) propenyloxy group and an active hydrogen group-containing compound. Examples of the active hydrogen-containing group include a hydroxyl group and an amino group.

Examples of the (meth) acryloxy group-containing compound include a compound represented by the following formula (3),

In formula (3), R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group, m3 and n3 each independently represent 1 to 5, and X is an active hydrogen-containing group. In formula (3), m3 and n3 are respectively the same as the formula (1) m and n are the same, and the active hydrogen-containing group X is the same as the above-mentioned active hydrogen-containing group.

Examples of the compound represented by the formula (3) include compounds represented by the following formula (3-1).

In the formula (3-1), R ³¹¹ , R ³¹² , m31, and n31 are the same as R ¹ , R ² , m, and n in the formula (1), respectively.

Specific examples of the compound represented by the formula (3) include 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate.

In the step 2, as the (meth) acryloxy group-containing compound, other (meth) acryloxy group-containing compounds may be used together with the compound represented by the formula (3). Examples of other (meth) acrylfluorenyl-containing compounds include compounds having one (meth) acrylfluorenyloxy group and an active hydrogen group-containing compound in one molecule.

As the other (meth) acrylic fluorenyloxy-containing compound, for example, Examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol (meth) acrylate, dipentaerythritol (meth) acrylate, Mono (meth) acrylic fluorenyloxy-containing compounds, such as tris (2-hydroxyethyl) isocyanurate mono (meth) acrylate), having one or more hydroxyl groups.

The production of the (meth) acrylic fluorenyloxy-containing compound is not particularly limited. For example, a conventionally well-known thing can be mentioned. Moreover, as a (meth) acryl fluorenyl group containing compound, a commercial item can be used. The compound represented by the above formula (3-1) can be produced according to the production method described in, for example, Japanese Patent Laid-Open No. 2007-28995.

The molar ratio of the compound represented by formula (3) to the total of the (meth) acryloxy-group-containing compounds used in step 2 (the compound represented by formula (3) / the compound used in step 2 The total amount of the (meth) acryloxy group-containing compound) is preferably 50 mol% or more.

The (meth) acrylic fluorenyloxy-containing compound may be used alone or in combination of two or more kinds.

The use amount of the (meth) acryloxy group-containing compound is preferably 1 to 100 parts by mass, and more preferably 1 to 50 parts by mass, with respect to 100 parts by mass of the isocyanate group-containing polymer.

In step 2, the polymer of the present invention can be prepared by mixing an isocyanate group-containing polymer and a (meth) acrylic fluorenyl group-containing compound, and then heating at 50 to 120 ° C.

The polymers prepared as above can also be mixtures. Examples of the mixture include two or more kinds of the polymer of the present invention and a polymer containing the present invention. And a polymer other than the polymer of the present invention (for example, polymer a) described later.

[Polymer composition containing (meth) acrylic acid]

By using the polymer of the present invention, a polymer composition (composition) containing a (meth) acrylic fluorenyloxy group can be prepared.

Examples of the composition include a composition containing a (meth) acrylic fluorenyl group-containing polymer (A) and a photopolymerization initiator.

In the above composition, a part or all of the polymer (A) (polymer (A)) containing a (meth) acrylic alkoxy group may be used as the polymer of the present invention.

<Poly (meth) acryloxy-containing polymer (A)>

The polymer used as part or all of the polymer (A) is the same as the polymer of the present invention described above. The polymer used as a part or all of the polymer (A) may be used alone or in combination of two or more kinds.

When a part of the polymer (A) is the polymer of the present invention, as the polymer (A), other (meth) acryloxy-group-containing polymers may be included. A) acryloxyoxy polymer a.

The polymer a has a main chain, and the main chain and the (meth) acrylfluorenyl group may be bonded directly or through a hetero atom or an organic group. The backbone, heteroatoms, and organic groups that the polymer a may have are the same as those described above. Examples of the (meth) acrylfluorenyl group which the polymer a has include a group (other group) having a (meth) acrylfluorenyl group different from the functional group described above.

The number average molecular weight of the polymer a is preferably 5,000 to 100,000, and more preferably 10,000 to 70,000. The number-average molecular weight of the polymer a is a value obtained by measuring by polystyrene conversion using gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

The production of the polymer a is not particularly limited. For example, the above-mentioned polymer a may be a by-product generated when the polymer of the present invention is produced. In addition, as a method for producing the polymer a, for example, in addition to replacing the compound represented by the above formula (3) with the other (meth) acrylic fluorenyloxy-containing compound in the above step 2, the present invention is similar to the present invention The method for producing a polymer is performed in the same manner as in the production of a polymer.

The polymer a can be used alone or in combination of two or more kinds.

When a part of the polymer (A) is the polymer of the present invention, the content of the polymer of the present invention is preferably 10 to 80% by mass, and more preferably 20 to 65% by mass, relative to the total amount of the polymer (A).

(Monofunctional (meth) acrylate compound)

In addition, as for the said composition, the thing containing the monofunctional (meth) acrylate compound which has one (meth) acryl methoxy group further is mentioned as one of the preferable aspects.

The monofunctional (meth) acrylate compound is not particularly limited as long as it is a compound having one (meth) acrylic fluorenyloxy group. The (meth) acrylfluorenyl group may be bonded to a hydrocarbon group. The hydrocarbon group is not particularly limited. For example, the same thing as the above is mentioned.

As specific examples of the monofunctional (meth) acrylate compound, Examples include meth (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and carbidine Alcohol (meth) acrylate, 2-ethylhexyl (meth) acrylate, epoxypropyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, Stearyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, allyl (meth) acrylate, 3-methoxybutyl (methyl Base) acrylate, isooctyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isofluorenyl (meth) acrylate, isodecyl (Meth) acrylates and the like. A monofunctional (meth) acrylate compound may be used individually by 1 type, and may use 2 or more types together.

Among these, in consideration of the good compatibility with the (meth) acryloxy group-containing polymer (A) and excellent weather resistance, it is more preferably selected from the group consisting of a compound having an alicyclic hydrocarbon group and a compound having a chain hydrocarbon group. At least one of the group consisting of a compound, a dicyclopentenyl (meth) acrylate, an isofluorenyl (meth) acrylate, and an isodecyl (meth) acrylate.

The content of the monofunctional (meth) acrylate compound is preferably 10 to 200 parts by mass, and more preferably 30 to 100 parts by mass relative to 100 parts by mass of the (meth) acryloxy group-containing polymer (A). Serving.

<Photopolymerization initiator>

Examples of the photopolymerization initiator include carbonyl compounds such as alkyl phenone compounds, benzoin ether compounds, and diphenyl ketone compounds, sulfur compounds, azo compounds, peroxide compounds, and phosphine oxides. Department of compounds and so on.

More specifically, for example, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyridine, toluene, benzyl, diphenyl ketone, p-formyl Oxydiphenyl ketone, diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, toluene glyoxylate, glyoxylate, 4,4'-bis (di Methylamine diphenyl ketone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, carbonyl compounds such as 1-hydroxycyclohexyl benzophenone represented by the following formula (8); Sulfur compounds such as methylthiuram and tetramethylthiuram disulfide; azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, etc .; benzamidine peroxide And peroxy compounds such as di-tert-butyl peroxide, etc. These may be used alone or in combination of two or more.

Among these, from the viewpoints of light stability, high efficiency of photofragmentation, compatibility with the (meth) acryloxy-group-containing polymer (A), low volatility, and low odor, it is preferably 1 -Hydroxycyclohexylbenzophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2 -Methyl-1-propane-1-one.

Examples of commercially available products of 1-hydroxycyclohexylbenzophenone include IRGACURE 184 (manufactured by Ciba Specialty Chemicals).

Relative to the above (meth) acrylic fluorenyl-containing polymer (A) 100 parts by mass, the content of the photopolymerization initiator is preferably 1 to 10 parts by mass, and more preferably 2 to 8 parts by mass.

(Solvent, additive)

From the viewpoint of workability, the composition may further contain a solvent.

Specific examples of the solvent include ethanol, isopropanol, butanol, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, and cyclohexanone.

The above-mentioned composition may further contain various additives as long as the object of the present invention is not impaired. Examples of the additives include polyfunctional (meth) acrylates other than the polymer of the present invention, plasticizers, fillers, anti-aging agents, antioxidants, antistatic agents, flame retardants, tackifiers, and leveling agents. Agents, dispersants, defoamers, matting agents, light stabilizers (for example, hindered amine compounds, etc.), dyes, pigments, and the like.

<Preparation method>

The method for preparing the above composition is not particularly limited. For example, the composition can be prepared by adding the above-mentioned various necessary components and optional components to a reaction container, and mixing them thoroughly using a stirrer such as a stirrer under reduced pressure.

The composition can achieve hardenability by light, for example. The light irradiated to the composition is not particularly limited. Examples include ultraviolet rays.

There are no particular restrictions on the temperature conditions at which the composition is cured. For example, it can be 0 to 150 ° C.

The composition can be used as an adhesive, for example. Specific examples of the adhesive include optical clear resin (OCR: Optical Clear Resin). The OCR can be adhered to a cover glass of a touch screen, a transparent conductive member, a liquid crystal module, and the like.

The substrate (adhesive) to which the above composition can be applied is not particularly limited. Examples include glass, plastic, rubber, and metal.

Examples

Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to these examples.

<Manufacture of (meth) acrylic fluorenyl-containing polymer>

In the production of the (meth) acrylic fluorenyl-containing polymer (the polymer of the present invention), each component shown in the table is used in the amount (unit g) shown in the first table.

First, each raw polymer is mixed with each polyisocyanate, and reacted at 70 ° C. for 5 hours under a nitrogen atmosphere to obtain an isocyanate group-containing polymer having an isocyanate group at both ends (step 1).

Then, when the residual NCO content is 0.96% or less, each (meth) acryloxy group-containing compound is added to the reaction system and reacted at 70 ° C for 5 hours to prepare (meth) acryloxy group Based polymer (step 2).

The polymer (A-1) containing the (meth) acrylic fluorenyloxy group prepared in Example 1 was used. In addition, the polymers made in other examples are as As shown in the table.

The structure of the (meth) acryloxy-group-containing polymer prepared as described above is shown by the following formula (5).

Formula (5): [functional group-urethane bond ⁵¹ -polyisocyanate residue-urethane bond ⁵² ] ₂ -base polymer residue

In formula (5), the base polymer residue corresponds to the main chain of the (meth) acrylic fluorenyl group-containing polymer. The polymer prepared as described above has a main chain derived from the base polymer. The main chain of the polymer produced as described above may also be a dimer or more having a raw polymer. At this time, in addition to the urethane bond ⁵¹ and the urethane bond ⁵² , the main chain of the polymer prepared as described above may include a urethane bond derived from the polyisocyanate used in the production .

Further, in the formula (5), the portion of "urethane bond ⁵¹ -polyisocyanate residue-urethane bond ⁵² " corresponds to an organic group.

Polymer (A-1)

The two functional groups possessed by the polymer (A-1) are both groups represented by the following formula (1-1).

The content 1 of the polymer (A-1) was 10 mol%, and the content 2 was 90 mol%.

The polyisocyanate residue is an isophorone diisocyanate residue.

The number average molecular weight of the polymer (A-1) was 23,000.

Polymer (A-2)

Both functional groups of the polymer (A-2) are represented by the above formula (1-1) The base.

The content 1 of the polymer (A-2) was 15 mol%, and the content 2 was 85 mol%.

The number average molecular weight of the polymer (A-2) was 23,000.

Polymer (A-3)

The polymer (A-3) is a mixture containing the polymer (A-3-1), the polymer (A-3-2), and the polymer (A-3-3).

The polymers (A-3-1) to (A-3-3) are all the same except for the functional group.

The content 1 of the polymer (A-3) was 35 mol%, and the content 2 was 65 mol%.

The polymer (A-3-1) has two functional groups each represented by the formula (1-1).

One functional group of the polymer (A-3-2) is a group represented by the above formula (1-1), and the remaining one is a group represented by the following formula (2-1).

Both of the functional groups possessed by the polymer (A-3-3) are groups represented by the formula (2-1).

Polymer (A-4)

The polymer (A-4) is a mixture containing the polymer (A-4-1), the polymer (A-4-2), and the polymer (A-4-3).

The polymers (A-4-1) to (A-4-3) are all the same except for the functional group.

The content 1 of the polymer (A-4) was 35 mol%, and the content 2 was 65 mol%.

Both of the functional groups possessed by the polymer (A-4-1) are groups represented by the following formula (1-2).

One functional group of the polymer (A-4-2) is a group represented by the above formula (1-2), and the remaining one is a group represented by the above formula (2-1).

The two functional groups of the polymer (A-4-3) are both groups represented by the above formula (2-1).

Polymer (A-5)

Both of the functional groups of the polymer (A-5) are groups represented by the formula (1-1).

The content 1 of the polymer (A-5) was 35 mol%, and the content 2 was 65 mol%. The polyisocyanate residue is a hexamethylene diisocyanate residue.

Polymer (A-6)

Both functional groups of the polymer (A-6) are those represented by the above formula (1-1) base.

The content 1 of the polymer (A-6) was 10 mol%, and the content 2 was 90 mol%. The polyisocyanate residue is an isophorone diisocyanate residue.

Polymer (A-7)

Both of the functional groups of the polymer (A-7) are groups represented by the formula (1-1).

The content (3) of the polymer (A-7) was 100 mol%. The polyisocyanate residue is an isophorone diisocyanate residue.

Comparative polymer (E-1)

Both functional groups of the comparative polymer (E-1) were groups represented by the formula (2-1).

The content of the comparative polymer (E-1) was 10 mol%, and the content 2 was 90 mol%. The polyisocyanate residue is an isophorone diisocyanate residue.

Comparative polymer (E-2)

Both functional groups of the comparative polymer (E-2) were groups represented by the following formula (2-2).

The content 1 of the comparative polymer (E-2) was 10 mol%, and the content 2 was 90 mol%. The polyisocyanate residue is an isophorone diisocyanate residue.

Each component shown in Table 1 is as follows.

In addition, content 4 is represented by the content of the repeating unit represented by Formula (Ia) with respect to the total of the repeating unit represented by Formula (Ia)-Formula (Ic) which comprises the main chain of each base polymer. The content of the repeating unit represented by the formula (Ib) represents a content of 5, and the content of the repeating unit represented by the formula (Ic) represents a content of 6.

(Manufacture of (meth) acrylic acid-containing compound 2)

According to the production method described in Japanese Patent Application Laid-Open No. 2007-28995 (Example 2), glycerol and methyl acrylate are subjected to a transesterification reaction in the presence of a lipase in a polar organic solvent to produce (meth) propylene Zingoxy compound 2.

<Manufacture of composition>

Each component shown in the following Table 3 or Table 5 was mixed with a mixer according to the composition (parts by mass) shown in the table to obtain each composition.

<Hardening of composition>

Each composition obtained as described above is cured under the curing conditions shown below to obtain a cured product.

(Hardening conditions)

Each composition was coated on a glass plate to a thickness of 0.3 mm to prepare a sample.

A light irradiation device (GS UVSYSTEM TYPE S250-01, manufactured by GS Yuasa lighting) was used, under conditions of 23 ° C under a nitrogen flow, at a light amount of 120 mW / cm and a cumulative light amount of 1000 mJ / cm ² . The sample was irradiated with ultraviolet light (light source: metal halide lamp, wavelength 250-380 nm) to harden the composition.

<Evaluation of polymerization degree>

FT-IR (Fourier transform infrared spectroscopy) was used to measure the samples before and after the hardening, and the degree of polymerization was evaluated according to the following method. The KBr tableting method was used to tablet the samples before and after hardening, and this was used as the sample for the above measurement.

The absorbance of 810 cm ^-1 of FT-IR is derived from the vinyl (double bond site) of (meth) acrylfluorenyl.

That is, the initial state (the peak intensity at 810 cm ^-1 is the strongest) before curing (the composition) is set to 0%, and the state after the curing (polymerization) is completely completed (the peak intensity at 810 cm ^-1 is 0). In the case of), the degree of polymerization is 100%. For the samples before and after the hardening, the measured absorbance of the peak intensity is substituted into the following formula to calculate the degree of polymerization. The results are shown in Tables 3 and 5.

Degree of polymerization (%) = 100- (Absorbance of the above peak intensity of the sample after hardening / Absorbance of the above peak intensity of the sample before hardening)

It is considered that the higher the degree of polymerization, the faster the hardening speed.

Each component shown in Table 3 is as follows.

From the results shown in Table 3, it can be seen that Comparative Examples 3 and 4 which do not contain a prescribed (meth) acrylic fluorenyl-containing polymer have a slow curing rate.

In contrast, Examples 8 to 16 have fast curing speeds.

In addition, when comparing Examples 8, 9, 12, 13 and Example 14, it can also be seen that the hardening speeds of Examples 8, 9, 12, 13 whose main chain is polybutadiene or its hydride are also Faster than Example 14 where the main chain was polyisoprene.

When comparing Examples 10 to 12, it can also be seen that the specific content of the (meth) acryloxy group-containing compound used in the production of the (meth) acryloxy group-containing polymer is specific. The larger the molar ratio of the (meth) acrylic fluorenyl compound, that is, the greater the amount of the prescribed functional group of the polymer of the present invention, the faster the hardening speed.

Each component shown in Table 5 is as follows.

From the results shown in Table 5, it can be seen that Comparative Examples 5 and 6 which do not contain the prescribed (meth) acrylic fluorenyl-containing polymer have a slow curing rate.

In contrast, Examples 17 to 28 have fast curing speeds.

In addition, when comparing Examples 22, 23, 26, and 27 with Example 28, it can also be seen that Examples 22, 23, 26, and 27 whose main chain is polybutadiene or its hydride are The polyisoprene Example 28 hardened faster.

In addition, when Example 22 is compared with Example 27, Example 22 whose main chain is a polybutadiene hydride hardens faster than Example 27 whose main chain is polybutadiene.

When comparing Examples 24 to 26, it can also be seen that the specific content of the (meth) acryloxy group-containing compound used in the production of the (meth) acryloxy group-containing polymer Compound of (meth) acrylic acid The larger the molar ratio of the material, that is, the greater the amount of the prescribed functional group that the polymer of the present invention has, the faster the hardening speed.

Claims (6)

A (meth) acryloxy-group-containing polymer having a backbone as a backbone and having a polymer composed of at least one monomer selected from the group consisting of butadiene and isoprene, or A hydride thereof, and having a functional group represented by the following formula (1) at the terminal, In formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, m and n each independently represent 1 to 5, and * represents a bonding position with the aforementioned main chain. For example, the (meth) acryloxy group-containing polymer according to claim 1, wherein the main chain and the functional group are bonded directly or through a hetero atom or an organic group. For example, the (meth) acryloxy group-containing polymer according to claim 2, wherein the organic group has two or more urethane bonds. The (meth) acrylic fluorenyl group-containing polymer according to any one of claims 1 to 3, wherein the skeleton has a group selected from the group consisting of repeating units represented by the following formulae (Ia) to (Ic) At least one of In the formulae (Ia) to (Ic), the double line of the dashed line and the solid line represents a single bond or a double bond. For example, the (meth) acrylic fluorenyl group-containing polymer according to claim 4, wherein the polymer represented by the aforementioned formula (Ia) is represented by the aforementioned formula (Ia) with respect to the total of the repeating units represented by the aforementioned formulas (Ia) to (Ic). The content of the repeating unit 1 is 0 to 40 mol%, and the content of the repeating unit 2 represented by the aforementioned formula (Ib) is 0 relative to the total of the repeating units represented by the aforementioned formula (Ia) to formula (Ic). The content of ~ 100 mole% is 0 ~ 100 mole% relative to the total of the repeating units represented by the aforementioned formula (Ia) ~ formula (Ic). The (meth) acrylic fluorenyloxy group-containing polymer according to any one of claims 1 to 3, wherein one or more molecules have (meth) acrylic fluorenyloxy groups.