Chain transfer agent, method for producing polymer, polymer, adhesive composition, and polymer particles

Abstract

Provided is a chain transfer agent other than a thiol compound, the molecular weight of which can be sufficiently controlled. According to the present invention, a chain transfer agent represented by formula (1) is provided. # imgabs0 # (In formula (1), X is a group selected from the group consisting of a cyano group, an optionally substituted aryl group, an acyl group, a carboxyl group, COOR1, C (O) NH2, C (O) NHR1, C (O) NR12, SOR1, SO2R1, SO3R1, and OR1, Y and Z are each a group selected from the group consisting of a cyano group, an optionally substituted aryl group, an acyl group, a carboxyl group, COOR1, C (O) NH2, C (O) NHR1, C (O) NR12, SOR1, SO2R1, SO3R1, OR1, OC (O) R1, N (H) C (O) R1, and a halogen, or Y and Z are bonded to form an optionally substituted carbocyclic structure or an optionally substituted heterocyclic structure, X, Y, and Z may be the same Q is hydrogen, an optionally substituted alkyl group having 1-6 carbon atoms, or a phenyl group, R2 and R3 are groups selected from the group consisting of hydrogen, an optionally substituted alkyl group having 2-6 carbon atoms, an optionally substituted aryl group, and an optionally substituted heterocyclic structure, and R2 and R3 may be the same as or different from each other (excluding the case where both R2 and R3 are hydrogen). ).

Description

[Technical field]

[0001] The present invention relates to a chain transfer agent, a method for producing a polymer, a polymer, an adhesive composition, and polymer particles. [Background technology]

[0002] (First point of view) When a radical polymerizable compound such as methyl methacrylate is polymerized, a chain transfer agent is used for the purpose of adjusting the molecular weight of the polymer, and a mercaptan compound such as n-dodecyl mercaptan has been conventionally used.

[0003] Patent Document 1 discloses a chain transfer agent composed of a compound having a maleimide group and a mercapto group, and Patent Document 2 discloses a thiol compound having a specific structure and discloses using the compound as a chain transfer agent.

[0004] (Second point of view) In addition, there is disclosed a technique for polymerizing polymers for various purposes using a sulfur-containing thiol chain transfer agent (e.g., sulfur such as n-dodecyl mercaptan). For example, Patent Document 3 discloses a method for producing (meth)acrylic acid-based crosslinked particles, which comprises a step of polymerizing monomer components including a (meth)acrylic acid alkyl ester and a (meth)acrylic acid multifunctional monomer in the presence of a thiol chain transfer agent. [Prior art literature] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2003-321506 [Patent Document 2] Japanese Patent Application Publication No. 2004-292428 [Patent Document 3] International Publication No. 2017 / 022423 [Summary of the invention] [Problems to be solved by the invention]

[0006] (First point of view) Thiol compounds have the advantage of being able to effectively control the molecular weight of polymers. On the other hand, thiol compounds have problems such as having a unique odor (peculiar smell) and being undesirable (bad) to use polymers obtained by using thiol compounds as chain transfer agents in certain application fields. In addition, although chain transfer agents other than thiol compounds have been developed, these cannot sufficiently control the molecular weight.

[0007] The present invention has been made in view of the above circumstances, and provides a chain transfer agent other than a thiol compound that can sufficiently control the molecular weight.

[0008] (Second point of view) Thiol compounds have the advantage of being able to effectively control the molecular weight of polymers. On the other hand, thiol compounds have problems such as having a unique odor (peculiar smell) and, in certain application fields, using thiol compounds as chain transfer agents and then polymerizing the resulting polymer may cause corrosion.

[0009] The present invention has been made in view of such circumstances, and provides a polymer that is less likely to cause corrosion problems than polymers using conventional thiol chain transfer agents such as thiol compounds, and provides a method for producing a polymer that is less likely to cause corrosion problems and can sufficiently control the molecular weight compared to the case of using conventional thiol chain transfer agents such as thiol compounds.

Methods to solve the problem

[0010] (First point of view) According to the present invention, there is provided a chain transfer agent represented by the following formula (1).

[0011]

Chemistry 1

[0012] In formula (1), X is selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , and OR 1 Y and Z are selected from cyano, arbitrarily substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , OR 1 、OC(O)R 1 、N(H)C(O)R 1 and a halogen group, or Y and Z are bonded to form an arbitrarily substituted carbocyclic structure or an arbitrarily substituted heterocyclic structure, X, Y, and Z may be the same or different, and R 1 is an optionally substituted alkyl group having 1 to 8 carbon atoms, Q is hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or phenyl, R 2 and R 3 is a group selected from hydrogen, an alkyl group having 2 to 6 carbon atoms, an optionally substituted aryl group, and an optionally substituted heterocyclic structure, R 2 and R 3They may be the same or different (but not including R 2 and R 3 are all hydrogen).

[0013] The present inventors have made intensive studies and have found that when a compound represented by the above formula (1) is used as a chain transfer agent to polymerize monomers to obtain a polymer, the molecular weight of the obtained polymer can be sufficiently controlled, thereby completing the present invention.

[0014] (Second point of view) According to the present invention, there is provided a polymer comprising a polymer chain having a group represented by the following formula (18) at the terminal.

[0015]

Chemistry 18

[0016] (In formula (18), X is selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , and OR 1 The group, R 1 is a group optionally substituted with an alkyl group having 1 to 8 carbon atoms, R 2 and R 3 is a group selected from hydrogen, an alkyl group having 2 to 6 carbon atoms, an optionally substituted aryl group, and an optionally substituted heterocyclic structure, R 2 and R 3 They may be the same or different (but not including R 2 and R 3 All are hydrogen. )

[0017] The present inventors have made careful studies and found that when a compound having a specific structure is used as a chain transfer agent to polymerize monomers to obtain a polymer, a polymer that is less likely to cause corrosion problems can be obtained compared to a polymer using a conventional thiol-based chain transfer agent such as a thiol compound, and that the molecular weight can be sufficiently controlled, thereby completing the present invention.

[0018] Various embodiments of the present invention are described below. The embodiments described below can be combined with each other. [1] A chain transfer agent represented by the following formula (1).

[0019]

Chemistry 1

[0020]

Chemistry 23

[0021]

Chemistry 18

[10] The polymer according to [9], wherein the group represented by the formula (18) is represented by the following formula (21).

[0022]

Chemistry 21

[11] The polymer according to [9] or

[10] , wherein the polymer chain having a group represented by the formula (18) at the terminal further has a group represented by the following formula (19) at the terminal.

[0023]

Chemistry 19

[12] The polymer according to

[11] , wherein the group represented by the formula (19) is represented by the following formula (22).

[0024]

Chemical formula 22

[13] The polymer according to [9] or

[10] , wherein the sulfur content derived from the mercaptan-based chain transfer agent in the polymer is 100 ppm or less.

[14] The polymer according to [9] or

[10] , wherein the polymer chain has repeating monomer units, and the repeating monomer units have at least one group selected from a carboxyl group, a hydroxyl group, an amino group, and an amide group.

[15] An adhesive composition comprising the polymer according to

[14] and at least one crosslinking agent selected from an isocyanate crosslinking agent, an epoxy crosslinking agent, and a metal chelate crosslinking agent..

[16] A polymer particle comprising the polymer according to [9] or

[10] , wherein the average particle diameter of the polymer particle is 0.05 to 500 μm.

Effects of the Invention

[0025] (First aspect) If the chain transfer agent of the present invention is used to polymerize monomers to produce polymers, a polymer with effectively controlled molecular weight can be obtained. In addition, according to the production method of the present invention, a polymer with fully controlled molecular weight can be obtained. In addition, compared with the chain transfer agent of a thiol compound, the chain transfer agent of the present invention has less odor. In addition, compared with the polymer polymerized using a thiol compound as a chain transfer agent, the use of the polymer polymerized using the chain transfer agent of the present invention is not limited.

[0026] (Second point of view) According to the present invention, a polymer that is less likely to cause corrosion problems than polymers using conventional thiol chain transfer agents such as thiol compounds is provided, and a method for producing a polymer that is less likely to cause the above problems than when conventional thiol chain transfer agents such as thiol compounds are used and that can sufficiently control the molecular weight is provided.

Brief Description of the Drawings

[0027] Figure 1 Shown are observation images obtained by observing the polymer particles of Example 2-10 and Example 2-12 using a microscope. Figure 2 Shown are observation images obtained by observing the polymer particles of Comparative Example 2-4 and Reference Example 2-6 using a microscope. [Specific implementation method]

[0028] The following examples illustrate the embodiments of the present invention and specifically describe the present invention. The present invention is not limited thereto. The various characteristic matters of the embodiments of the present invention shown below can be combined with each other. Moreover, each characteristic matter independently establishes the invention.

[0029] 1. Chain transfer agent The chain transfer agent of the present invention has a structure represented by the following formula (1).

[0030]

Chemistry 1

[0031] In formula (1), X is selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , and OR 1 The group.

[0032] The reaction mechanism when the compound represented by formula (1) functions as a chain transfer agent for free radical polymerization can be explained as follows. First, an addition reaction occurs in which the vinylene group is attacked by a free radical species, and then a cleavage reaction occurs with the recombination of the double bond and the elimination of the allyl substituent (i.e., the methyl group substituted by Q, Y, or Z), generating a methyl radical substituted by Q, Y, or Z. This series of reaction mechanisms is called an addition-cleavage reaction, in which X determines the ease with which the addition reaction occurs, and Y, Z, and R determine the ease with which the addition reaction occurs. 2 and R 3 Determines the ease with which the cleavage reaction occurs. In addition, it is preferred to select the best X according to the assumed monomer. When reinitiation reaction is expected to occur by free radical species released by chain transfer reaction, it is preferred to select the best Q, Y, and Z according to the assumed monomer. 2 , R 3 form and its working principle.

[0033] In one embodiment of the present invention, X can be a cyano group. When X is a cyano group, the inductive effect of the nitrogen atom and the resonance effect of the cyano group and the vinylidene group play a role, and produce a deviation of the electron density (polarization) between the 2 carbon atoms constituting the vinylidene group. As a result, vinylidene easily accepts the addition of free radical species. In addition, if a free radical is added to the vinylidene group, a new free radical species will be generated, but the cyano group also has the function of delocalizing the unpaired electrons of the free radical by the resonance effect, and stabilizing the free radical species. That is to say, compared with X being a hydrogen atom or a non-conjugated olefin as an alkyl, when X is a cyano group, it is very easy to cause free radical addition.

[0034] In one embodiment of the present invention, X may be an arbitrarily substituted aryl group. The aryl group may be a monocyclic ring, a condensed ring formed by condensation of two or more aromatic rings, or a connected ring connected by two or more aromatic rings. The number of carbon atoms of the aromatic ring constituting the aryl group may be 6 to 18, preferably 6 to 12, and more preferably 6 to 10. Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, and 4-biphenyl, and the aryl group is preferably phenyl. The aryl group may have a substituent, and examples of the substituent include an alkyl group having 1 to 8 carbon atoms, a cyano group, a carboxyl group, and the like. When X is an arbitrarily substituted aryl, the resonance effect of aryl and vinylidene comes into play, and produces the deviation (polarization) of electron density between 2 carbon atoms constituting vinylidene. As a result, vinylidene easily accepts the addition of free radical species. In addition, if free radical is added on vinylidene, new free radical species will be generated, but aryl also has the function of making the unpaired electron delocalization of this free radical by resonance effect, and making the free radical species stable. In addition, when aryl is substituted by alkyl, cyano or carboxyl, the large resonance effect or hyperconjugation effect comprising these substituents comes into play, and compared to unsubstituted aryl, free radical is further stabilized. As can be seen from the above, when X is a hydrogen atom or as the non-conjugated olefin of alkyl compared with X, free radical addition is very easily caused when X is an arbitrarily substituted aryl.

[0035] In one embodiment of the present invention, X may be an acyl group (C(=O)R 1 ), carboxyl, COOR 1 、amide (C(O)NH2、C(O)NHR 1 , or C(O)NR 1 2) SOR containing sulfone substituent 1 、SO2R 1 、SO3R 1 Examples of the acyl group include formyl, acetyl, propionyl, and benzoyl. 1 That is, alkoxycarbonyl (R 1 OC(=O)) includes, for example, methoxycarbonyl, ethoxycarbonyl, and tert-butoxycarbonyl. Among the amide groups, N-substituted amide groups (C(O)NHR 1 , or C(O)NR 1 2), for example, R 1 is an N-substituted amide group of methyl, ethyl, n-propyl, or isopropyl. When X is an acyl group (C(=O)R 1 ), carboxyl, COOR 1 、amide (C(O)NH2、C(O)NHR 1 , or C(O)NR 1 2) SOR containing sulfone substituent 1 、SO2R 1 、SO3R 1When the inductive effect of the oxygen atom of the carbonyl / sulfone group and the resonance effect of the carbonyl / sulfone group and the vinylidene group act, a deviation (polarization) of the electron density occurs between the two carbon atoms constituting the vinylidene group. As a result, the vinylidene group is easily subjected to the addition of free radical species. In addition, if a free radical is added to the vinylidene group, a new free radical species will be generated, but the carbonyl / sulfone group also has the function of delocalizing the unpaired electrons of the free radical through the resonance effect and stabilizing the free radical species. In other words, when X is a hydrogen atom or a non-conjugated olefin as an alkyl group, X is more likely to be an acyl group (C(=O)R 1 ), carboxyl, COOR 1 、amide (C(O)NH2、C(O)NHR 1 , or C(O)NR 1 2) SOR containing sulfone substituent 1 、SO2R 1 、SO3R 1 When it is reacted with water, it is very easy to cause free radical addition.

[0036] In one embodiment of the present invention, X can be OR 1 When X is OR 1 When X is a hydrogen atom or a non-conjugated olefin as an alkyl group, the inductive effect of the oxygen atom and the resonance effect of the oxygen atom and the vinylidene group play a role, and a deviation (polarization) of the electron density is generated between the two carbon atoms constituting the vinylidene group. As a result, the vinylidene group is easily subjected to the addition of free radical species. In other words, compared with the non-conjugated olefin as X is a hydrogen atom or an alkyl group, X is OR 1 When it is used, it is easy to cause free radical addition.

[0037] R 1 It is a group arbitrarily substituting an alkyl group having 1 to 8 carbon atoms. The number of carbon atoms of the alkyl group having 1 to 8 carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, or 8, and may also be in the range between any two values ​​exemplified here. The alkyl group having 1 to 8 carbon atoms may be linear or branched. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, octyl, isooctyl, and 2-ethylhexyl. The alkyl group is preferably a methyl, ethyl, or propyl group. R 1 It may be arbitrarily substituted, and examples of the substituent include hydroxyl, isocyanate, carboxyl, amino, sulfo, and alkoxysilyl. The group arbitrarily substituted with the alkyl group having 1 to 8 carbon atoms may be selected from unsubstituted alkyl, (CH2)nOH, (CH2)nNCO, (CH2)nCOOH, (CH2)nNH2, (CH2)nSO3H, (CH2)nOSi(OR 4Here, n can be a natural number from 1 to 8, R 4 The group may be an alkyl group having 1 to 8 carbon atoms.

[0038] The above-mentioned X has the effect of promoting the free radical addition to vinylidene, but in addition to this, it is preferred to consider the compatibility with the monomer used (such as a free radical polymerizable compound). The compatibility of the monomer and X can be judged by the copolymerization of the monomer with the substituted vinyl compound represented by CH2=C(H)X. When the monomer is M1 and the substituted vinyl compound is M2, the monomer reactivity ratio r1 represented by the Mayo-Lewis formula is preferably 0.1 to 5, more preferably 0.3 to 2, and further preferably 0.5 to 1.5. For example, when X is an acetoxy group, the above-mentioned substituted vinyl compound is vinyl acetate. Since the reactivity ratio of styrene to vinyl acetate is r1=22, the chain transfer agent in which X is an acetoxy group will hardly play a role in the polymerization system of styrene, and is therefore not preferred. On the other hand, when X is COOCH3, the above-mentioned substituted vinyl compound is methyl acrylate. Since the reactivity ratio of styrene to methyl acrylate is r1=0.75, the chain transfer agent in which X is a COOCH3 group is preferred in the polymerization system of styrene. When a substituted vinyl compound represented by CH2=C(H)X is used as a monomer, the monomer M1 is the same as the substituted vinyl compound M2 to be compared, so r1=1. That is, it is most preferred to select X that is the same as the substituent of the monomer used. For example, the chain transfer agent used in the polymerization system of methyl acrylate is most preferably X=COOCH3. The chain transfer agent of one embodiment of the present invention is a chain transfer agent used in the polymerization of the monomer M1, and the monomer M1 preferably contains X as a substituent. It should be noted that X may not contain sulfur.

[0039] Y and Z are each selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , OR 1 , and a halogen group, or Y and Z may be bonded to form an arbitrarily substituted carbocyclic structure or an arbitrarily substituted heterocyclic structure. As specific examples of aryl and acyl, the same specific examples as those listed in the description of X may be cited.

[0040] In one embodiment of the present invention, Y and / or Z are groups that determine the ease with which the free radical added to the vinylidene group undergoes a cleavage reaction. The more effective Y and / or Z are in stabilizing the free radicals on the carbon atoms bonded to the vinylidene group, the more likely it is to cause a cleavage reaction. Thus, the group that can delocalize unpaired electrons through the resonance effect of Y and / or Z is preferably selected from cyano, arbitrarily substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 、OC(O)R 1 、N(H)C(O)R 1 and halogen groups.

[0041] In one embodiment of the present invention, Y and / or Z also determine the ease of occurrence of the reinitiation reaction of the free radical species released by the cleavage reaction. Regarding the ease of occurrence of the reinitiation reaction, if the monomer represented by CH2=C(Y)Z is M2 and the monomer used for polymerization is M1, the monomer reactivity ratio r2 represented by the Mayo-Lewis formula of the copolymer is 0 to 5, it will easily occur, if it is 0 to 2, it will be more likely to occur, and if it is 0 to 1, it will be particularly easy to occur. However, even in the case of a so-called destructive chain transfer reaction in which no reinitiation reaction occurs at all, the purpose of adjusting the molecular weight can be successfully achieved. Therefore, Y and / or Z are preferably selected according to the ease of occurrence of the cleavage reaction described in the previous paragraph, and the selection range is not limited by the presence or absence of the reinitiation reaction.

[0042] Y and / or Z may include R 1 It is a group arbitrarily substituting an alkyl group having 1 to 8 carbon atoms. The number of carbon atoms of the alkyl group having 1 to 8 carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, or 8, and may also be in the range between any two values ​​exemplified here. The alkyl group having 1 to 8 carbon atoms may be linear or branched. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, octyl, isooctyl, and 2-ethylhexyl. The alkyl group is preferably a methyl, ethyl, or propyl group. R 1It may be arbitrarily substituted, and examples of the substituent include hydroxyl, isocyanate, carboxyl, amino, sulfo, and alkoxysilyl. The group arbitrarily substituted with an alkyl having 1 to 8 carbon atoms may be selected from unsubstituted alkyl, (CH2)nOH, (CH2)nNCO, (CH2)nCOOH, (CH2)nNH2, (CH2)nSO3H, (CH2)nOSi(OR 4 Here, n can be a natural number from 1 to 8, R 4 The group may be an alkyl group having 1 to 8 carbon atoms.

[0043] Y and Z may also be a carbon ring structure or a hetero ring structure which is optionally substituted and formed by bonding Y and Z. The carbocyclic structure may be a cycloalkyl group having 3 to 8 carbon atoms. The heterocyclic structure may be a 3- to 8-membered heterocyclic ring. The heterocyclic ring has at least one heteroatom selected from N, O, and S, or may have two or more heteroatoms. Furthermore, the heterocyclic ring preferably has at least one O atom. The carbocyclic structure and the heterocyclic structure may have a substituent, and examples of the substituent include an alkyl group having 1 to 8 carbon atoms, a cyano group, a carboxyl group, an oxy group, a halogen group, etc. The substituent preferably includes an oxy group. In one embodiment of the present invention, Y and Z may also be bonded to form McLennan's acid or a McLennan's acid derivative.

[0044] X, Y, and Z can be different. Furthermore, regarding X, Y, and Z, at least two of X, Y, and Z may be the same, Y and Z may be the same, or Y and Z may be the same, but X may be different. X, Y, and Z may all be the same.

[0045] Q is hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group. Q may be an optionally substituted alkyl group having 1 to 6 carbon atoms, and examples of the substituent include cyano, carboxyl, halogen, hydroxyl, alkoxy, and amino. Q is preferably hydrogen.

[0046] R 2 and R 3 is a group selected from hydrogen, an alkyl group having 2 to 6 carbon atoms, an optionally substituted aryl group, and an optionally substituted heterocyclic structure, but excluding R 2 and R 3 When R 2 and R 3 When all R are hydrogen, a terminal olefin is produced by chain transfer reaction. 2 and R 3When at least one of is selected from an alkyl group having 2 to 6 carbon atoms, an arbitrarily substituted aryl group, and an arbitrarily substituted heterocyclic structure, an internal olefin is generated by a chain transfer reaction. Due to the hyperconjugation effect or resonance effect of the substituent, the internal olefin is more stable than the terminal olefin. 2 With R 3 Compared with hydrogen chain transfer agents, they produce more stable internal olefins and R 2 and R 3 A chain transfer agent in which at least one of the groups selected from an alkyl group having 2 to 6 carbon atoms, an arbitrarily substituted aryl group, and an arbitrarily substituted heterocyclic group is more likely to undergo a chain transfer reaction. 2 or R 3 The stabilization of olefins and the increase of steric hindrance near olefins inhibit the re-attack of free radical species thermodynamically and kinetically, respectively. As a result, the chain transfer reaction can be made irreversible and the generation of branched and cross-linked structures starting from the generated olefin terminal can be inhibited. In this way, R 2 and R 3 It has the effect of promoting the chain transfer reaction and inhibiting the side reaction caused by the olefin terminal generated after the chain transfer.

[0047] R 2 and / or R 3 It can be an alkyl group having 2 to 6 carbon atoms. The number of carbon atoms of the alkyl group is, for example, 2, 3, 4, 5, or 6, and can also be in the range between any two values ​​exemplified here. The alkyl group having 2 to 6 carbon atoms can be straight-chain or branched. Examples of the alkyl group include ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, and 2-ethylbutyl. Since when R 2 and / or R 3 When it is a methyl group, an internal olefin is also generated, and in terms of promoting chain transfer reactions, it can be expected that the same effect as alkyl groups with 2 to 6 carbon atoms such as ethyl groups can be achieved. However, the steric hindrance of the methyl group is not sufficient to inhibit the attack of free radicals on the olefin terminal generated after chain transfer. This can be judged from the following: methyl crotonate (an internal olefin substituted with a methyl group at the β position of methyl acrylate) undergoes free radical copolymerization with other vinyl monomers. Thus, R 2 and / or R 3 A larger alkyl group having 2 to 6 carbon atoms is preferred, and sec-butyl, tert-butyl and isopropyl are particularly preferred.

[0048] R 2 and / or R 3It can be any substituted aromatic group. When the internal olefin is generated by chain transfer reaction, the aromatic group can resonate with the olefin. The formation of a long and stable conjugated system has the effect of promoting the chain transfer reaction while inhibiting the reverse reaction. The resonance effect has a significantly higher stabilizing effect on the olefin than the hyperconjugation effect of the alkyl group, so R 2 and / or R 3 Preferably, it is an aryl group. The aryl group may be a monocyclic ring, a condensed ring of 2 or more aromatic rings condensed, or a connected ring of 2 or more aromatic rings connected. The number of carbon atoms of the aromatic ring constituting the aryl group may be 6 to 18, preferably 6 to 12, and more preferably 6 to 10. As the aryl group, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, and 4-biphenyl may be mentioned, and the aryl group is preferably phenyl. The aryl group may have a substituent, and as the substituent, for example, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, a carboxyl group, a halogen, etc. may be mentioned. In particular, resonance with the aromatic ring by a cyano group, a carboxyl group, a halogen, etc. has the effect of further expanding the conjugated system generated by the chain transfer reaction, and is particularly preferred because it can strongly promote the chain transfer reaction.

[0049] R 2 and R 3 It may be an optionally substituted heterocyclic structure. The heterocyclic structure may be a 3- to 8-membered heterocyclic ring. The heterocyclic ring has at least one heteroatom selected from N, O, and S, and may have two or more heteroatoms. The heterocyclic structure may have a substituent, and examples of the substituent include an alkyl group having 1 to 8 carbon atoms, a cyano group, a carboxyl group, a halogen group, and the like. When the heterocyclic ring is aliphatic, similarly to the alkyl group, the effect of promoting the chain transfer reaction derived from the stabilization of the internal olefin of the hyperconjugation and the effect of suppressing the formation of the branched and cross-linked structure can be expected. When the heterocyclic ring is aromatic, similarly to the aryl group, the effect of promoting the chain transfer reaction of the internal olefin stabilization based on the resonance effect and the effect of suppressing the formation of the branched and cross-linked structure can be expected.

[0050] Furthermore, in one embodiment of the present invention, if R 2 With R 3 If the steric hindrance of is too large, the free radical addition to the vinylidene group is inhibited, and the chain transfer constant is reduced. Therefore, from the perspective of obtaining appropriate reactivity, R 2 With R 3 Among them, at least one is preferably hydrogen.

[0051] In formula (1), the chain transfer agent of one embodiment of the present invention is preferably designed to select appropriate X, Y, Z, Q, R according to the structure of the monomer used in the polymerization or whether a reinitiation reaction occurs. 2 , R 3For example, in the free radical polymerization system of acrylic esters, when designing a chain transfer agent including reinitiation reaction, X is selected from cyano, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , and phenyl groups, Y and Z are cyano, carboxyl, COOR 1 、C(O)R 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , and phenyl groups, X, Y, Z can be the same or different, the R 1 is an alkyl group having 1 to 8 carbon atoms, Q is hydrogen or methyl, R 2 and R 3 One of them may be hydrogen, and the other may be a group selected from an alkyl group having 2 to 6 carbon atoms, an optionally substituted aryl group, and an optionally substituted heterocyclic structure. In which, from the viewpoint of the ease of chain transfer or the compatibility and solubility with monomers and polymers, X is selected from cyano, COOR 1 and a phenyl group, Y and Z are selected from cyano, COOR 1 , and phenyl groups, X, Y, Z can be the same or different, the R 1 is an alkyl group having 1 to 8 carbon atoms, Q is hydrogen or methyl, R 2 and R 3 One of them is preferably hydrogen, and the other is preferably a group selected from an alkyl group having 2 to 6 carbon atoms, an optionally substituted aryl group, and an optionally substituted heterocyclic structure. In addition, from the viewpoint of synthesis, X is selected from cyano, COOR 1 A group, Y, Z are selected from cyano, COOR 1 , and phenyl groups, X, Y, Z can be the same or different, the R 1 is an alkyl group having 1 to 8 carbon atoms, Q is a methyl group, R 2 and R 3 Hydrogen is particularly preferred, and phenyl is particularly preferred.

[0052] The chain transfer agent according to one embodiment of the present invention has a structure represented by the following formula (1), and may have a skeleton represented by the formula (23) described later.

[0053] The chain transfer agent having a skeleton represented by the following formula (23) is described below.

[0054]

Chemistry 23

[0055] When the compound represented by formula (23) functions as a chain transfer agent for free radical polymerization, the reaction mechanism can be explained as follows. First, an addition reaction of the vinylene group to accept a free radical species occurs, followed by a cleavage reaction to generate a polymer chain having an end represented by formula (21), and it is believed that a free radical represented by the following formula (24) is generated. And, the regrowth of the polymer begins by the generation of the free radical represented by formula (24). This series of reaction mechanisms is called an addition-cleavage reaction, where X is related to the ease of the addition reaction, and R is related to the ease of the addition reaction. 51 , R 52 , and R 6 and R 21 , R 22 , R 23 , R 24 , and R 25 It is related to the ease of occurrence of the cleavage reaction. Here, it is preferred to select the optimal X according to the assumed monomer. When reinitiation reaction is expected by the free radical species released by the chain transfer reaction, it is preferred to select the optimal R according to the assumed monomer. 51 , R 52 , and R 6 .

[0056]

Chemistry 24

[0057] In formula (23), X is selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , and OR 1 The group.

[0058] In one embodiment of the present invention, X can be cyano group.When X is cyano group, the inductive effect of nitrogen atom and the resonance effect of cyano group and vinylidene group play a role, and produce the deviation (polarization) of electron density between 2 carbon atoms constituting vinylidene group.As a result, vinylidene group is easy to accept the addition of free radical species.In addition, if the addition free radical on vinylidene group, new free radical species will be generated, but cyano group also has the function of making the unpaired electron of the free radical delocalized by the resonance effect, and making the free radical species stabilized.That is to say, compared with X being a hydrogen atom or a non-conjugated olefin as an alkyl, when X is cyano group, it is very easy to cause free radical addition.

[0059] In one embodiment of the present invention, X can be an arbitrarily substituted aryl group. The aryl group can be a monocyclic ring, a condensed ring of 2 or more aromatic rings condensed, or a connected ring of 2 or more aromatic rings connected. The number of carbon atoms of the aromatic ring constituting the aryl group can be 6 to 18, preferably 6 to 12, and more preferably 6 to 10. As an aryl group, for example, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, and 4-biphenyl can be listed, and the aryl group is preferably a phenyl group. The aryl group may have a substituent, and as a substituent, for example, an alkyl group, a cyano group, a carboxyl group, etc. having a carbon number of 1 to 8 can be listed. When X is an arbitrarily substituted aryl group, the resonance effect of the aryl group and the vinylidene group plays a role, and a deviation (polarization) of the electron density is generated between the two carbon atoms constituting the vinylidene group. As a result, the vinylidene group is easily subjected to the addition of free radical species. In addition, if a free radical is added to the vinylidene group, a new free radical species will be generated, but the aryl group also has the function of delocalizing the unpaired electrons of the free radical through the resonance effect and stabilizing the free radical species. In addition, when the aryl group is substituted by an alkyl group, a cyano group or a carboxyl group, the large resonance effect and hyperconjugation effect of these substituents play a role, and the free radical is further stabilized compared to the unsubstituted aryl group. As can be seen from the above, when X is an arbitrarily substituted aryl group, free radical addition is very likely to occur compared to a non-conjugated olefin in which X is a hydrogen atom or an alkyl group.

[0060] In one embodiment of the present invention, X may be an acyl group (C(=O)R 1 ), carboxyl, COOR 1 、amide (C(O)NH2、C(O)NHR 1 , or C(O)NR 1 2) SOR containing sulfone substituent 1 、SO2R 1 、SO3R 1 In one embodiment of the present invention, X may be an acyl group (C(=O)R 1 ), carboxyl, COOR 1 、amide (C(O)NH2、C(O)NHR 1 , or C(O)NR 12) As the acyl group, for example, formyl, acetyl, propionyl, and benzoyl can be mentioned. 1 That is, alkoxycarbonyl (R 1 OC(=O)) includes, for example, methoxycarbonyl, ethoxycarbonyl, and tert-butoxycarbonyl. Among the amide groups, N-substituted amide groups (C(O)NHR 1 , or C(O)NR 1 2), for example, R 1 is an N-substituted amide group of methyl, ethyl, n-propyl, or isopropyl. When X is an acyl group (C(=O)R 1 ), carboxyl, COOR 1 、amide (C(O)NH2、C(O)NHR 1 , or C(O)NR 1 2) SOR containing sulfone substituent 1 、SO2R 1 、SO3R 1 When the carbonyl group / sulfone group is added to the vinylene group, the inductive effect of the oxygen atom of the carbonyl group / sulfone group and the resonance effect of the carbonyl group / sulfone group and the vinylene group act to produce a deviation (polarization) in electron density between the two carbon atoms constituting the vinylene group. As a result, the vinylene group is easily subjected to the addition of free radical species. In addition, if a free radical is added to the vinylene group, a new free radical species will be generated, but the carbonyl group / sulfone group also has the function of delocalizing the unpaired electrons of the free radical through the resonance effect and stabilizing the free radical species. In other words, compared with a non-conjugated olefin in which X is a hydrogen atom or an alkyl group, the acyl group (C(=O)R 1 ), carboxyl, COOR 1 、amide (C(O)NH2、C(O)NHR 1 , or C(O)NR 1 2) SOR containing sulfone substituent 1 、SO2R 1 、SO3R 1 When it is reacted with water, it is very easy to cause free radical addition.

[0061] In one embodiment of the present invention, X can be OR 1 When X is OR 1 When X is a hydrogen atom or a non-conjugated olefin as an alkyl group, the inductive effect of the oxygen atom and the resonance effect of the oxygen atom and the vinylidene group play a role, and a deviation (polarization) of the electron density is generated between the two carbon atoms constituting the vinylidene group. As a result, the vinylidene group is easily subjected to the addition of free radical species. That is, compared with the non-conjugated olefins in which X is a hydrogen atom or an alkyl group, the 1 When it is used, it is easy to cause free radical addition.

[0062] R 1It is a group that arbitrarily replaces an alkyl group having 1 to 8 carbon atoms. The number of carbon atoms in the alkyl group having 1 to 8 carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, or 8, and may also be in the range between any two values ​​exemplified here. The alkyl group having 1 to 8 carbon atoms may be linear or branched. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, octyl, isooctyl, and 2-ethylhexyl. The alkyl group is preferably a methyl, ethyl, or propyl group. R 1 It may be arbitrarily substituted, and examples of the substituent include hydroxyl, isocyanate, carboxyl, amino, sulfo, and alkoxysilyl. The substituent may be selected from any one of hydroxyl, isocyanate, carboxyl, amino, and alkoxysilyl. The group arbitrarily substituted with the alkyl group having 1 to 8 carbon atoms may be selected from unsubstituted alkyl, (CH2)nOH, (CH2)nNCO, (CH2)nCOOH, (CH2)nNH2, (CH2)nSO3H, (CH2)nOSi(OR 4 Here, n can be a natural number from 1 to 8, R 4 The group may be an alkyl group having 1 to 8 carbon atoms.

[0063] The above-mentioned X has the effect of promoting free radical addition to vinylidene groups, and in addition, it is preferably selected according to the compatibility with the monomer used (for example, free radical polymerizable compound). The compatibility of the monomer and X can be judged by the copolymerization of the monomer and the substituted vinyl compound represented by CH2=C(H)X. When the monomer is M1 and the substituted vinyl compound is M2, the monomer reactivity ratio r1 represented by the Mayo-Lewis formula is preferably 0.1-5, more preferably 0.3-2, and further preferably 0.5-1.5. For example, when X is an acetoxy group, the above-mentioned substituted vinyl compound is vinyl acetate. Since the reactivity ratio of styrene to vinyl acetate is r1=22, the chain transfer agent in which X is an acetoxy group has almost no effect in the polymerization system of styrene, and is therefore not preferred. On the other hand, when X is COOCH3, the above-mentioned substituted vinyl compound is methyl acrylate. Since the reactivity ratio of styrene to methyl acrylate is r1=0.75, the chain transfer agent in which X is a COOCH3 group is preferred in the polymerization system of styrene. When a substituted vinyl compound represented by CH2=C(H)X is used as a monomer, since the monomer M1 is the same as the substituted vinyl compound M2 to be compared, r1=1. That is, it is most preferred to select X that is the same as the substituent of the monomer used. For example, in the chain transfer agent used in the polymerization system of methyl acrylate, X=COOCH3 is most preferred. The chain transfer agent of one embodiment of the present invention is preferably a chain transfer agent used in the polymerization of the monomer M1, and the monomer M1 contains X as a substituent. It should be noted that X may not contain sulfur.

[0064] In one embodiment of the present invention, COOR 51 and / or COOR 52 It is a group that determines the ease with which the free radical added to the vinylidene group undergoes a cleavage reaction. 51 and / or COOR 52 The more effective it is in stabilizing the free radicals on these bonded carbon atoms, the easier it is to cause the cleavage reaction. 51 and / or COOR 52 The resonance effect delocalizes the unpaired electrons in the group.

[0065] In one embodiment of the present invention, COOR 51 and / or COOR 52 It also determines the ease of reinitiation of the free radical species released by the cleavage reaction. 51 )COOR 52When the monomer represented by the copolymer is M2 and the monomer used for polymerization is M1, the monomer reactivity ratio represented by the Mayo-Lewis formula is 0 to 5, which is easy to occur, 0 to 2, and 0 to 1. However, even in the case of a so-called destructive chain transfer reaction in which no reinitiation reaction occurs, the purpose of adjusting the molecular weight can be achieved smoothly. 51 and / or COOR 52 It is preferably selected based on the ease of occurrence of the cleavage reaction described in the preceding paragraph, and the selection range is not limited by the presence or absence of a reinitiation reaction.

[0066] R 51 and R 52 is an alkyl group having 1 to 8 carbon atoms, R 51 and R 52 They may be the same or different. The number of carbon atoms in the alkyl group having 1 to 8 carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, or 8, and may also be within the range between any two values ​​exemplified here. The alkyl group having 1 to 8 carbon atoms may be linear or branched. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, octyl, isooctyl, and 2-ethylhexyl.

[0067] R 6 R is hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group. 6 It may be an optionally substituted alkyl group having 1 to 6 carbon atoms, and examples of the substituent include cyano, carboxyl, halogen, hydroxyl, alkoxy, and amino. 6 Preferred is methyl.

[0068] In formula (23), R 21 , R 22 , R 23 , R 24 , and R 25 is a group selected from hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, a carboxyl group, and a halogen group, and R 21 , R 22 , R 23 , R 24 , and R 25They may be the same or different. The number of carbon atoms in the alkyl group having 1 to 8 carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, or 8, and may also be in the range between any two values ​​exemplified here. The alkyl group having 1 to 8 carbon atoms may be linear or branched. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, octyl, isooctyl, and 2-ethylhexyl. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy. Examples of the halogen include fluorine, chlorine, bromine, and iodine. R 21 , R 22 , R 23 , R 24 , and R 25 Preferred is hydrogen.

[0069] In one embodiment of the present invention, the chain transfer agent having a skeleton represented by the above formula (23) may not contain sulfur.

[0070] The chain transfer agent of the present invention can be used when polymerizing a radical polymerizable compound, and the weight average molecular weight of the obtained polymer can be adjusted to, for example, 5,000 to 2,000,000. The weight average molecular weight of the polymer is, for example, 5,000, 10,000, 30,000, 50,000, 100,000, 200,000, 500,000, 1,000,000, 1,500,000, 2,000,000, and may be within the range between any two of the values ​​exemplified here.

[0071] 2. Method for producing chain transfer agent The method for producing the chain transfer agent of the present invention is not particularly limited as long as a chain transfer agent having a structure represented by the above formula (1) can be obtained.

[0072] As an example, the chain transfer agent of the present invention can be obtained by reacting a compound represented by the following formula (2) with a halogen compound represented by formula (3) (as an example, a bromine compound) in the presence of a solvent and a base.

[0073]

Chemistry 2

[0074]

Chemistry 3

[0075] In the above formulas (2) and (3), X, Y, Z, Q, and R 2 , R 3 Respectively with X, Y, Z, Q, R in the above formula (1) 2 , R 3 same.

[0076] As the solvent, tetrahydrofuran (THF), dichloromethane, chloroform, acetone, 2-butanone, acetonitrile, toluene, ethyl acetate, butyl acetate, methanol, ethanol, or the like can be used. As the base, 1,4-diazabicyclo[2.2.2]octane (DABCO), triethylamine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), pyridine and the like can be used.

[0077] 3. Method for producing polymer using chain transfer agent 3.1 Polymerization process The method for producing a polymer of the present invention includes a polymerization step of polymerizing a radical polymerizable compound in the presence of the above-mentioned chain transfer agent. According to the production method of the present invention, a polymer having a controlled molecular weight can be obtained.

[0078] In the polymerization process of one embodiment of the present invention, one or more chain transfer agents having a skeleton represented by the above formula (23) may be used. In the polymerization process of one embodiment of the present invention, chain transfer agents having a skeleton represented by the above formula (23) and other chain transfer agents other than chain transfer agents having a skeleton represented by the above formula (23) may also be used in combination.

[0079] As other chain transfer agents, 2-mercaptoethanol, thioglycerol, 3-mercaptohexan-1-ol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptopropionic acid, 6-mercaptohexanoic acid, 11-mercaptodecanoic acid, 3-mercaptopyruvic acid, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptobenzoic acid, thiomalic acid, n-dodecyl mercaptan, pentaerythritol tetrakis (3-mercaptopropionate), α-methylstyrene dimer, and naphthoquinone compounds.

[0080] In the polymerization step of one embodiment of the present invention, when the chain transfer agent used in the polymerization step is 100 mass %, the chain transfer agent composed of the skeleton represented by the above formula (23) may be contained at least 50 mass %, for example, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 mass %, and may be within the range between any two of the values ​​exemplified here.

[0081] In the polymerization process of one embodiment of the present invention, when the chain transfer agent used in the polymerization process is 100% by mass, the content of the thiol chain transfer agent can be, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50% by mass, or can be within the range between any two values ​​exemplified here. The thiol chain transfer agent can refer to a chain transfer agent containing sulfur such as a thiol compound as a thiol group, for example, a chain transfer agent containing sulfur as a sulfone group may not be included. In addition, the chain transfer agent of the structure of formula (23) of the present invention may not be included in the thiol chain transfer agent. The mercaptan chain transfer agent may include 2-mercaptoethanol, thioglycerol, 3-mercaptohexan-1-ol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptopropionic acid, 6-mercaptohexanoic acid, 11-mercaptodecanoic acid, 3-mercaptopyruvic acid, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptobenzoic acid, thiomalic acid, and n-dodecyl mercaptan. In the polymerization process of one embodiment of the present invention, a mercaptan chain transfer agent may not be used. In the polymerization process of one embodiment of the present invention, a sulfur-containing chain transfer agent may not be used. In addition, in the polymerization process of one embodiment of the present invention, as a chain transfer agent, only a chain transfer agent composed of a skeleton represented by the above formula (23) may be included.

[0082] In the polymerization process of one embodiment of the present invention, the amount of the chain transfer agent used can be appropriately adjusted according to the type of free radical polymerizable compound used and other polymerization conditions. It is not particularly limited, but it can be 0.001 to 10 parts by mass relative to 100 parts by mass of the free radical polymerizable compound. The amount of the chain transfer agent used is, for example, 0.001 parts by mass, 0.002 parts by mass, 0.005 parts by mass, 0.01 parts by mass, 0.02 parts by mass, 0.05 parts by mass, 0.1 parts by mass, 0.2 parts by mass, 0.5 parts by mass, 1.0 parts by mass, 5.0 parts by mass, 10.0 parts by mass, and can also be within the range between any two values ​​exemplified here.

[0083] In the polymerization step of one embodiment of the present invention, the amount of the chain transfer agent used can be 0.01 mmol to 200 mmol relative to 1 mol of the radical polymerizable compound. The amount of the chain transfer agent used is, for example, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, 2, 5, 10, 20, 50, 100, 150, 200 mmol relative to 1 mol of the radical polymerizable compound, and may also be within the range between any two values ​​exemplified here.

[0084] <Radical polymerizable compounds> The free radical polymerizable compound may include one having an ethylenically unsaturated bond. Examples of the compound having an ethylenically unsaturated bond include alkyl (meth)acrylates, carboxyl-containing monomers, hydroxyl-containing monomers, amino-containing monomers, amide-containing monomers, styrene-based monomers, cyano-containing monomers, monomers having two or more ethylenically unsaturated groups in one molecule, and derivatives thereof.

[0085] Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, n-heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate.

[0086] Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, β-carboxyethyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, mono(meth)acryloyloxyethyl succinate, ω-carboxypolycaprolactone mono(meth)acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid.

[0087] Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, methyl (4-hydroxymethylcyclohexyl)acrylate, N-hydroxymethyl (meth)acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether.

[0088] Examples of the amino group-containing monomer include N,N-dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminoalkyl (meth)acrylate and N,N-diethylaminoethyl methacrylate.

[0089] Examples of the amide group-containing monomer include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-hexyl(meth)acrylamide and other N-alkyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, (meth)acryloylmorpholine and the like.

[0090] Examples of the styrene monomers include styrene; alkyl styrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, and dibromostyrene; and functionalized styrenes such as nitrostyrene, acetylstyrene, and methoxystyrene.

[0091] Examples of the cyano group-containing monomer include cyano(meth)acrylate and (meth)acrylonitrile.

[0092] Examples of the monomer having two or more ethylenically unsaturated groups in one molecule include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and divinylbenzene.

[0093] The radical polymerizable compound may be used alone or in combination of two or more. The type and amount of the radical polymerizable compound may be appropriately selected depending on the desired physical properties of the polymer.

[0094] <Polymerization initiator> In the polymerization step, a polymerization initiator may be used. Examples of the polymerization initiator include thermal polymerization initiators and photopolymerization initiators. Examples of thermal polymerization initiators include organic peroxides and azo compounds. Examples of photopolymerization initiators include aromatic ketone compounds and benzoin compounds.

[0095] In the polymerization step of one embodiment of the present invention, an azo initiator can be used. Examples of the azo initiator include 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis(1-cyclohexylcarbonitrile) (ACHN), 2,2'-dimethyl azobisisobutyrate (MAIB), and 4,4'-azobis(4-cyanovaleric acid) (ACVA).

[0096] Examples of the peroxide polymerization initiator include tert-butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, hexanoyl peroxide, diisopropyl peroxide, di-2-ethylhexyl peroxydicarbonate, tert-butyl peroxydivalerate, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, 2,2-bis(4,4-di-tert-amylperoxycyclohexyl)propane, 2,2-bis(4,4-di-tert-octylperoxycyclohexyl)propane, 2,2-bis(4,4-di-α-cumylperoxycyclohexyl)propane, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)butane, 2,2-bis(4,4-di-tert-octylperoxycyclohexyl)butane, ammonium persulfate, potassium persulfate, and sodium persulfate.

[0097] In the polymerization step of one embodiment of the present invention, the polymerization initiator may be used alone or in combination of two or more. The polymerization initiator may be used in an amount of 0.001 to 5 parts by mass based on 100 parts by mass of the radical polymerizable compound.

[0098] <Solvent> In the polymerization step according to one embodiment of the present invention, a known solvent can be used. As an example, the solvent used for polymerization includes aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenethyl ether, and diphenyl ether; halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; and sulfoxides such as dimethyl sulfoxide and cyclopentane. In the polymerization step of one embodiment of the present invention, the adhesive composition can be obtained by a production method including the following polymerization step, wherein a radical polymerizable compound is polymerized in one or more organic solvents selected from ethyl acetate, ethyl methyl ketone, and toluene. As an example, the adhesive composition of one embodiment of the present invention can be obtained by polymerizing a radical polymerizable compound in one or more organic solvents selected from ethyl acetate, ethyl methyl ketone, and toluene.

[0099] Furthermore, as another example, in the polymerization step of one embodiment of the present invention, the radical polymerizable compound can be polymerized in an aqueous medium. The aqueous medium refers to water or a medium with water as the main component. Specifically, water alone or a mixture of lower alcohols such as methanol or ethanol and water can be cited, but water alone is preferred. As an example, the polymer particles of one embodiment of the present invention can be obtained by a polymerization step comprising polymerizing the radical polymerizable compound in an aqueous medium.

[0100] The weight average molecular weight of the polymer obtained by the above production method is, for example, 5000 to 2 million. The weight average molecular weight of the polymer is, for example, 5000, 10,000, 30,000, 50,000, 100,000, 200,000, 500,000, 1 million, 1.5 million, 2 million, or may be within the range between any two values ​​exemplified here.

[0101] 3.2 Other compound mixing process Depending on the purpose, the manufacturing method of one embodiment of the present invention may include a compound mixing step of adding a necessary compound to the obtained polymer. As an example, the manufacturing method of one embodiment of the present invention may include a polymerization step and a crosslinking agent mixing step, in which at least one crosslinking agent selected from an isocyanate crosslinking agent, an epoxy crosslinking agent, and a metal chelate crosslinking agent may be mixed with the obtained polymer. As described below, in particular, when the polymer is used as an adhesive composition, a crosslinking agent mixing step may be included.

[0102] As the crosslinking agent, isocyanate crosslinking agents, epoxy crosslinking agents, and metal chelate crosslinking agents can be cited. As the isocyanate crosslinking agent, an isocyanate crosslinking agent having an isocyanate group number of 2 or more in one molecule can be used. The polymer is crosslinked by the isocyanate crosslinking agent, thereby forming a crosslinked body.

[0103] The number of isocyanate groups of the isocyanate crosslinking agent may be 2 or more, preferably 2 to 8, and more preferably 3 to 6. If the number of isocyanate groups is within the above range, it is preferred from the viewpoint of the crosslinking reaction efficiency between the polymer and the isocyanate crosslinking agent and the aspect of maintaining the flexibility of the adhesive layer.

[0104] Among isocyanate crosslinking agents, from the viewpoint of good adhesive performance balance and high durability, reaction products of trimethylolpropane and toluene diisocyanate (L-45 manufactured by Soken Chemical, etc.), reaction products of trimethylolpropane and xylene diisocyanate (TD-75 manufactured by Soken Chemical, etc.), isocyanurates of hexamethylene diisocyanate or toluene diisocyanate (TSE-100 manufactured by Asahi Chemical, Coronate 2050 manufactured by Tosoh, etc.) can be used. One type of isocyanate crosslinking agent may be used alone, or two or more types may be used.

[0105] As the epoxy crosslinking agent, for example, an epoxy compound having 2 or more epoxy groups in one molecule can be used. For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl meta-xylylenediamine, N,N,N',N'-tetraglycidylaminophenylmethane, triglycidyl isocyanurate, meta-N,N-diglycidylaminophenylglycidyl ether, N,N-diglycidyltoluidine, and N,N-diglycidylaniline can be used. The epoxy crosslinking agent can be used alone or in combination of two or more.

[0106] Examples of the metal chelate crosslinking agent include compounds in which alkoxide, acetylacetone, ethyl acetoacetate, and the like are coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium.

[0107] Among them, aluminum chelate compounds are particularly preferred. Specifically, aluminum isopropoxide, aluminum sec-butyrate, aluminum ethyl acetoacetate diisopropoxide, aluminum triethyl acetoacetate, and aluminum triacetylacetonate. The metal chelate crosslinking agent may be used alone or in combination of two or more.

[0108] In the crosslinking agent mixing step, the crosslinking agent may be mixed in an amount of 0.01 to 5 parts by mass, preferably 0.03 to 4.5 parts by mass, and more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the polymer. A composition containing the polymer obtained by the method for producing a polymer of the present invention and a crosslinking agent can be used as a pressure-sensitive adhesive composition.

[0109] 4. Polymer The polymer according to one embodiment of the present invention has a polymer chain derived from a chain transfer agent represented by the above formula (1). The polymer according to one embodiment of the present invention includes a polymer chain having a group represented by the following formula (18) at the terminal.

[0110]

Chemistry 18

[0111] In formula (18), X is selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , and OR 1 The group, R 1is a group optionally substituted with an alkyl group having 1 to 8 carbon atoms, R 2 and R 3 is a group selected from hydrogen, an alkyl group having 2 to 6 carbon atoms, an optionally substituted aryl group, and an optionally substituted heterocyclic structure, R 2 With R 3 They may be the same or different (but not including R 2 With R 3 ) X, R 1 , R 2 and R 3 For the implementation methods, please refer to the above description.

[0112] The group represented by the formula (18) of the polymer according to one embodiment of the present invention can be represented by the following formula (21). That is, the polymer according to one embodiment of the present invention includes a polymer chain having a group represented by the following formula (21) at the terminal.

[0113]

Chemistry 21

[0114] In formula (21), R 21 , R 22 , R 23 , R 24 , and R 25 is a group selected from hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, a carboxyl group, and a halogen group, and R 21 , R 22 , R 23 , R 24 , and R 25 They can be the same or different. X is selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , and OR 1 The group, the R 1 It is a group optionally substituted by an alkyl group having 1 to 8 carbon atoms. R 21 , R 22 , R 23 , R 24 , and R 25 ,X,R 1 The implementation method is as described above.

[0115] In the polymer of one embodiment of the present invention, the polymer chain having a group represented by the formula (18) at the terminal may further have a group represented by the following formula (19) at the terminal.

[0116]

Chemistry 19

[0117] Y and Z are each selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , OR 1 、OC(O)R 1 、N(H)C(O)R 1 and a halogen group, or Y and Z are bonded to form an arbitrarily substituted carbocyclic structure or an arbitrarily substituted heterocyclic structure. Y and Z can be the same or different. 1 It is a group optionally substituted by an alkyl group having 1 to 8 carbon atoms. Q is hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group.

[0118] In the polymer according to one embodiment of the present invention, the group represented by the formula (19) can be represented by the formula (22). That is, in the polymer of one embodiment of the present invention, the polymer chain having a group represented by the following formula (21) at the terminal further has a group represented by the following formula (22) at the terminal.

[0119]

Chemistry 22

[0120] In formula (22), R 51 and R 52 is an alkyl group having 1 to 8 carbon atoms, R 51 and R 52 They can be the same or different. R 6 It is hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group. R 51 and R 52 , R 6 The implementation method is as described above.

[0121] The polymer having the terminal structure described above can be obtained by polymerizing a radical polymerizable compound in the presence of a chain transfer agent represented by a specific skeleton, specifically formula (1), especially formula (23). As described above, the reaction mechanism when the compound represented by formula (1), especially formula (23), functions as a chain transfer agent for free radical polymerization is considered to be that first, an addition reaction of vinylene groups to free radical species occurs, followed by a cleavage reaction to generate free radicals. Hereinafter, the case of using a compound represented by formula (23) is used as an example for explanation. In this process, first, a polymer chain having a terminal structure represented by formula (21) can be generated. Furthermore, the polymer chain can have a terminal structure represented by formula (21) at one end, and can have a terminal structure represented by formula (22) or a terminal structure derived from an initiator at the other end. Therefore, the polymer of one embodiment of the present invention may include a polymer chain having a group represented by the following formula (21) at the terminal. A polymer chain having a group represented by the formula (21) at one end and a group represented by the formula (22) at the other end, and / or A polymer chain having a group represented by the formula (21) at one terminal and having a terminal structure derived from an initiator at the other terminal. In addition, the polymer according to one embodiment of the present invention may have a polymer chain other than the polymer chain having the above structure.

[0122] In the polymer of one embodiment of the present invention, the sulfur content derived from the thiol chain transfer agent may be 100 ppm or less. In the polymer of one embodiment of the present invention, the sulfur content derived from the thiol chain transfer agent is, for example, 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 ppm, or may be within the range between any two values ​​exemplified here. Regarding the thiol chain transfer agent, as described above. The polymer of one embodiment of the present invention may not contain a -C-S-C- structure, which may generally be contained in the polymer obtained when the thiol chain transfer agent is used for polymerization.

[0123] In the polymer of one embodiment of the present invention, the total sulfur content in the polymer, including sulfur derived from the chain transfer agent of the structure of formula (23) of the present invention or derived from a radical polymerizable compound, may be 100 ppm or less. The sulfur content in the polymer of one embodiment of the present invention is, for example, 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 ppm, and may also be within the range between any two of the values ​​exemplified here.

[0124] In the polymer of one embodiment of the present invention, the sulfur content derived from the mercaptan chain transfer agent conventionally used in the polymerization of the polymer is low, and therefore problems due to sulfur, such as corrosion problems, are less likely to occur.

[0125] The polymer of one embodiment of the present invention may have a repeating monomer unit, and may include a repeating monomer unit derived from a free radical polymerizable compound. As the free radical polymerizable compound, the above-mentioned free radical polymerizable compound can be listed, and compounds with ethylenically unsaturated bonds can be listed. As compounds with ethylenically unsaturated bonds, for example, (meth) alkyl acrylates, carboxyl-containing monomers, hydroxyl-containing monomers, amino-containing monomers, amide-containing monomers, styrene-based monomers, cyano-containing monomers, monomers with two or more ethylenically unsaturated groups in one molecule, and derivatives thereof can be listed.

[0126] In the polymer of one embodiment of the present invention, the repeating monomer unit may have at least one group selected from carboxyl, hydroxyl, amino, and amide. Here, the carboxyl, hydroxyl, amino, and amide may be derived from a free radical polymerizable compound. In other words, the polymer of one embodiment of the present invention may have a repeating monomer unit derived from at least one monomer selected from carboxyl-containing monomers, hydroxyl-containing monomers, amino-containing monomers, and amide-containing monomers. When the polymer described later is used as an adhesive composition, it is particularly preferred that the repeating monomer unit has at least one group selected from carboxyl, hydroxyl, amino, and amide.

[0127] The weight average molecular weight (Mw) of the polymer of one embodiment of the present invention is, for example, 1000 to 2 million. The weight average molecular weight of the polymer is, for example, 1000, 2000, 3000, 5000, 10,000, 200,000, 300,000, 500,000, 100,000, 200,000, 300,000, 500,000, 1 million, 1.2 million, 1.3 million, 1.4 million, 1.5 million, 1.6 million, 1.7 million, 1.8 million, 1.9 million, 2 million, and may be within the range between any two values ​​exemplified here.

[0128] The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn) of the polymer of one embodiment of the present invention may be, for example, 1.1 to 4.5. The Mw / Mn of the polymer may be, for example, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, or may be within the range between any two of the values ​​exemplified here.

[0129] The polymer of the present invention is less likely to cause corrosion problems, and therefore, utilizing this property, it can be used as a material for various applications. As an example, the polymer of one embodiment of the present invention can be used in a binder composition and polymer particles.

[0130] 5. Adhesive composition The adhesive composition according to one embodiment of the present invention contains the above-mentioned polymer. The adhesive composition of one embodiment of the present invention preferably comprises the above-mentioned polymer and at least one crosslinking agent selected from the group consisting of an isocyanate crosslinking agent, an epoxy crosslinking agent, and a metal chelate crosslinking agent. Examples of the isocyanate crosslinking agent, the epoxy crosslinking agent, and the metal chelate crosslinking agent include the above-mentioned isocyanate crosslinking agent, the epoxy crosslinking agent, and the metal chelate crosslinking agent. The adhesive composition according to one embodiment of the present invention includes a polymer having a repeating monomer unit having at least one group selected from a carboxyl group, a hydroxyl group, an amino group, and an amide group, and includes the crosslinking agent, and improves adhesive properties by forming a crosslinked body.

[0131] The adhesive composition of one embodiment of the present invention may contain 0.01 to 5 parts by weight of a crosslinking agent relative to 100 parts by weight of the polymer. The content of the crosslinking agent is, for example, 0.01, 0.05, 0.1, 0.2, 0.30.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 parts by weight, or may be within the range between any two of the values ​​exemplified here.

[0132] The PSA composition according to one embodiment of the present invention may contain, in addition to the crosslinking agent, a known compound that can be added to a PSA composition such as a tackifying resin.

[0133] The method for producing the adhesive composition of one embodiment of the present invention is not particularly limited, but preferably includes a crosslinking agent mixing step, which is a step of mixing at least one crosslinking agent selected from isocyanate crosslinking agents, epoxy crosslinking agents, and metal chelate crosslinking agents in the polymer of the present invention. The method for producing the polymer of the present invention preferably includes a polymerization step, which is a polymerization step of polymerizing a radical polymerizable compound in the presence of a chain transfer agent composed of a skeleton represented by formula (23) and a polymerization initiator. The radical polymerizable compound preferably includes at least one monomer selected from carboxyl-containing monomers, hydroxyl-containing monomers, amino-containing monomers, and amide-containing monomers. The polymerization step is preferably a polymerization step of polymerizing the radical polymerizable compound in one or more organic solvents selected from ethyl acetate, ethyl methyl ketone, and toluene. In the polymerization step, the polymerization reaction can be carried out under standing or under stirring, but is preferably carried out under stirring. The polymerization temperature depends on the type and amount of the monomer components, the type and amount of the chain transfer agent and the polymerization initiator, but is preferably in the range of 30 to 100°C, and more preferably in the range of 40 to 90°C. The polymerization temperature may be constant from the beginning to the end of the polymerization, or may be varied within the above range. The polymerization temperature may be controlled only by the heat of reaction, or by external heating and cooling. The polymerization time is not particularly limited, but is preferably in the range of 1 to 30 hours, more preferably 2 to 15 hours. In addition, monomer components, chain transfer agents, polymerization initiators, and solvents may be appropriately added during the polymerization process.

[0134] The adhesive sheet of one embodiment of the present invention may include an adhesive layer and a substrate formed by the above-mentioned adhesive composition. As the adhesive sheet, for example, a two-sided adhesive sheet having only the above-mentioned adhesive layer, a two-sided adhesive sheet having a substrate and the above-mentioned adhesive layer formed on both sides of the substrate, a one-sided adhesive sheet having a substrate and the above-mentioned adhesive layer formed on one side of the substrate, and an adhesive sheet not attached with a release sheet, wherein the release sheet is attached to the surface that is not in contact with the substrate of the adhesive layer of these adhesive sheets.

[0135] Examples of the substrate and release sheet include plastic films such as polycarbonate (PC), polymethyl methacrylate (PMMA), polymethyl methacrylate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), polyamide (nylon), polyimide, and polyvinyl chloride (PVC). Examples of the substrate include glass, paper, and nonwoven fabrics.

[0136] The adhesive layer can be obtained by applying the above-mentioned adhesive composition on the release treatment surface of the substrate or the release sheet and removing the solvent by heating. The heating conditions can be adjusted according to the type of solvent. The heating temperature can be, for example, 50 to 150° C. And, the heating time can be, for example, 1 to 10 minutes. The thickness of the dried coating can be, for example, 5 to 100 μm.

[0137] After the release sheet is attached to the coating film formed under the above conditions, the pressure-sensitive adhesive layer may be aged in an environment of 5 to 60° C. and 30 to 70% RH for 3 days or more.

[0138] The adhesive composition can be applied to a predetermined thickness by a known method such as spin coating, doctor blade coating, roll coating, bar coating, blade coating, die coating, or gravure coating, and then dried.

[0139] 6. Polymer particles The polymer particles of one embodiment of the present invention include the above-mentioned polymer. The average particle size of the polymer particles is preferably 0.05 to 500 μm. The average particle size is, for example, 0.05, 0.10, 0.20, 0.50, 1, 2, 5, 10, 20, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500 μm, and may be within the range between any two values ​​exemplified here. The average particle size may be the average particle size measured by the method described in the examples.

[0140] The polymer particles of one embodiment of the present invention preferably have a CV value of 2 to 80%. For example, it is 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80%, or may be within the range between any two of the values ​​exemplified here. It should be noted that the CV value can be calculated by the following formula. CV value = standard deviation / average particle size × 100

[0141] The method for producing polymer particles according to one embodiment of the present invention is not particularly limited, but preferably includes a polymerization step, which is a step of polymerizing a radical polymerizable compound in the presence of a chain transfer agent composed of a skeleton represented by formula (23) and a polymerization initiator, and the polymerization step is preferably a step of polymerizing a radical polymerizable compound in an aqueous solvent. In addition, in the polymerization step, known compounds such as an emulsifier, a dispersant, and an antioxidant may be added as needed.

[0142] In the polymerization step, the polymerization reaction can be carried out under standing or under stirring, preferably under stirring. The polymerization temperature depends on the type and amount of the monomer components, the type and amount of the chain transfer agent and the polymerization initiator, but is preferably in the range of 30 to 100°C, more preferably in the range of 40 to 90°C. The polymerization temperature can be constant from the beginning to the end of the polymerization, or it can be changed within the above range. The polymerization temperature can be controlled only by the heat of reaction, or it can be controlled by heating and cooling from the outside. The polymerization time is not particularly limited, but is preferably in the range of 1 to 30 hours, more preferably in the range of 2 to 15 hours.

[0143] The generated polymer particles are preferably separated from the aqueous medium. The method for separation from the aqueous medium is not particularly limited, and known methods can be appropriately applied. As separation methods, filtration, vacuum filtration, centrifugation, spray drying, freeze drying and evaporative drying can be listed. As required, the polymer particles separated from the aqueous medium can also be further dried and crushed or crushed as required. [Example]

[0144] Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited thereto.

[0145] (First point of view) Chain transfer agents CTA1 to 4 were synthesized by the following procedure. Synthesis of CTA1 (chain transfer agent of Comparative Example 1) In a 200 ml two-necked eggplant flask, 27.58 ml (74.9 mmol) of a 20 wt% sodium ethoxide solution (manufactured by Tokyo Chemical Industry) and 100 ml of ethanol (manufactured by Junsei Chemical Industry) were added and immersed in an ice bath. While stirring, 11.3 ml (74.9 mmol) of compound (4) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise to obtain solution (1). In another 500 ml two-necked eggplant flask, 20 ml of ethanol and 14.38 g (74.9 mmol) of compound (5) (manufactured by Tokyo Chemical Industry) were added dropwise to the flask while the temperature in the flask was kept below 10°C. After the addition of dropwise addition, the mixture was stirred for 3 hours. Then, 100 ml of water and 200 ml of dichloromethane (manufactured by Yoneyama Pharmaceutical Industry) were added to extract the organic layer, and the mixture was washed twice with 100 ml of a saturated sodium chloride aqueous solution. Then, the mixture was dehydrated with magnesium sulfate (manufactured by Yoneyama Pharmaceutical Industry), and the solvent was distilled off under reduced pressure to obtain CTA1 represented by formula (6).

[0146]

Chemistry 4

[0147]

Chemistry 5

[0148]

Chemistry 6

[0149] Synthesis of CTA2 (chain transfer agent of Comparative Example 2) In a 200 ml two-necked eggplant flask, 7.73 ml (21 mmol) of a 20 wt% sodium ethoxide solution and 10 ml of ethanol were added and immersed in an ice bath. While stirring, 3.58 ml (21 mmol) of compound (7) (manufactured by Tokyo Chemical Industry) was added dropwise to obtain solution (2). In another 200 ml two-necked eggplant flask, 20 ml of ethanol and 2.92 ml (21 mmol) of compound (5) were added dropwise and immersed in an ice bath. While keeping the temperature in the flask below 10°C, solution (2) was added dropwise. After the addition of dropwise addition, stirring was performed for 4 hours. Then, 100 ml of water and 100 ml of dichloromethane were added to extract the organic layer, and the mixture was washed twice with 100 ml of a saturated sodium chloride aqueous solution. Then, dehydration was performed with sodium sulfate, and the solvent was distilled off under reduced pressure to collect a crude product of CTA2. The crude product of CTA2 was purified by silica gel column chromatography (Wakogel C400-HG, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) using hexane / ethyl acetate as a developing solvent to obtain CTA2 represented by formula (8).

[0150]

Chemistry 7

[0151]

Chemistry 8

[0152] Synthesis of CTA3 (chain transfer agent of Example 1) <Synthesis of Compound (11)> In a 500 ml eggplant flask, 40 ml of acetonitrile (produced by Yoneyama Pharmaceutical Co., Ltd.) and 10 ml of ethanol were added, followed by the addition of 60 ml (564 mmol) of compound (9) (produced by Tokyo Chemical Industry Co., Ltd.), 31.6 ml (314 mmol) of compound (10) (produced by Fujifilm Wako Pure Chemical Industries, Ltd.) and 17.6 g (157 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO) (produced by Tokyo Chemical Industry Co., Ltd.) to dissolve the mixture. The eggplant flask was immersed in an oil bath at 70°C and stirred for 24 hours. Then, the mixture was concentrated under reduced pressure at 50°C, 200 ml of dichloromethane and 100 ml of water were added to extract the organic layer, and the organic layer was washed twice with 300 ml of saturated sodium chloride aqueous solution. Then, dehydration was performed with magnesium sulfate, and the solvent was distilled off under reduced pressure to collect the crude product of compound (11). The collected crude product was purified by silica gel column chromatography (Wakogel C400-HG, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) using hexane / ethyl acetate as a developing solvent to obtain compound (11).

[0153]

Chemistry 9

[0154]

Chemistry 10

[0155]

Chemistry 11

[0156] <Synthesis of Compound (12)> 150 ml of dichloromethane and 15 g (75 mmol) of compound (11) were added to a 500 ml two-necked eggplant flask, and the flask was immersed in an ice bath. 8.5 ml (90 mmol) of tribromophosphine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise. After the addition was completed, the temperature in the flask was kept below 15°C and stirred for 1 hour. Next, 50 ml of water was added, and 100 ml of saturated sodium bicarbonate aqueous solution was injected while the temperature in the flask was kept below 15°C to extract the organic layer, and the organic layer was washed twice with 100 ml of saturated sodium chloride aqueous solution. Next, dehydration was performed with magnesium sulfate, and the solvent was removed by distillation under reduced pressure to obtain compound (12).

[0157]

Chemistry 12

[0158] <Synthesis of CTA3> In a 100 ml two-necked eggplant flask, 40 ml of THF (ultra-dehydrated grade, manufactured by Kanto Chemical) and 1.52 g (38.1 mmol) of sodium hydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (60 wt% in oil) were added and immersed in an ice bath. Then, compound (4) was added dropwise while the temperature in the flask was maintained below 10°C. After the addition was completed, the temperature of the flask was adjusted to 25°C and stirred for 30 minutes to obtain a solution (3). In another 200 ml two-necked eggplant flask, 40 ml of THF and 10 g (37.1 mmol) of compound (12) were added and stirred, and 1.5 g (44.6 mmol) of DABCO was added and immersed in an ice bath. While the temperature in the flask was maintained below 10°C, solution (3) was added dropwise, and stirred for 3 hours after the addition was completed. Next, 200 ml of dichloromethane, 50 ml of water and 100 ml of saturated sodium chloride water were added to extract the organic layer, and the organic layer was washed twice with 100 ml of saturated sodium chloride aqueous solution. Next, dehydration was performed using magnesium sulfate, and the solvent was removed by vacuum distillation to obtain a crude product of CTA3. The crude product of CTA3 was purified using silica gel column chromatography (Wakogel C400-HG manufactured by Fujifilm Wako Pure Chemical Industries) using hexane / ethyl acetate as a developing solvent to obtain CTA3 represented by formula (13).

[0159]

Chemistry 13

[0160] <Synthesis of CTA4> <Synthesis of Compound (15)> In a 300 ml two-necked eggplant flask, 20 ml of acetonitrile, 16.38 ml (250 mmol) of compound (14) (manufactured by Tokyo Chemical Industry), 20.0 ml (198 mmol) of compound (10) and 22.43 g (200 mmol) of DABCO were added and dissolved. The eggplant flask was immersed in an oil bath at 50°C and stirred for 13 hours. Then, the mixture was concentrated under reduced pressure at 50°C, 150 ml of dichloromethane and 80 ml of water were added, and the organic layer was extracted and washed twice with 150 ml of saturated sodium chloride aqueous solution. Then, the mixture was dehydrated with magnesium sulfate, and the solvent was distilled off under reduced pressure to collect a crude product of compound (15). The crude product of compound (15) was purified by silica gel column chromatography (Wakogel C400-HG, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) using hexane / ethyl acetate as a developing solvent to obtain compound (15).

[0161]

Chemistry 14

[0162]

Chemistry 15

[0163] <Synthesis of Compound (16)> 150 ml of dichloromethane and 5.0 g (31.4 mmol) of compound (14) were added to a 500 ml double-necked eggplant flask and immersed in an ice bath. 3.32 ml (35 mmol) of tribromophosphine was added dropwise. After the addition was completed, the temperature in the flask was maintained below 15°C and stirred for 1 hour. Then, 30 ml of water was added dropwise, and 50 ml of saturated sodium bicarbonate aqueous solution was injected while the temperature in the flask was maintained below 15°C to extract the organic layer. The organic layer was washed twice with 70 ml of saturated sodium chloride aqueous solution. Then, after dehydration with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain compound (16).

[0164]

Chemistry 16

[0165] <Synthesis of CTA4> In a 50 ml two-necked eggplant flask, 10 ml of THF (ultra-dehydrated grade, manufactured by Kanto Chemical) and 0.72 g (18.0 mmol) of sodium hydride (60 wt% in oil) were added and immersed in an ice bath. Then, 3.01 ml (17.6 mmol) of compound (7) was added dropwise while the temperature in the flask was kept below 10°C. After the addition was completed, the temperature of the flask was adjusted to 25°C and stirred for 30 minutes to obtain a solution (4). In another 300 ml two-necked eggplant flask, 190 ml of acetonitrile and 3.9 g (17.6 mmol) of compound (16) were added and stirred, and then 1.974 g (17.6 mmol) of DABCO was added and immersed in an ice bath. While the temperature in the flask was kept below 10°C, solution (4) was added dropwise, and stirred for 3 hours after the addition was completed. Next, 200 ml of dichloromethane, 250 ml of water and 100 ml of saturated sodium chloride aqueous solution were added to extract the organic layer, and the organic layer was washed twice with 200 ml of saturated sodium chloride aqueous solution. Next, dehydration was performed using magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product of CTA4. The crude product of CTA4 was purified by silica gel column chromatography using hexane / ethyl acetate as a developing solvent to obtain CTA4 represented by formula (17).

[0166]

Chemistry 17

[0167] Using the chain transfer agents CTA1 to 4 obtained above, polymers were produced. <Production of polymers> (Example 1-1) In a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 100 parts by mass (0.78 mol) of butyl acrylate (BA), 0.32 parts by mass (0.87 mmol) of CTA3, and 130 parts by mass of ethyl acetate were added, and the temperature was raised to 70° C. while introducing nitrogen. Next, 0.1 parts by mass of 2,2'-azobisisobutyronitrile was added, and a polymerization reaction was carried out at 70° C. for 3 hours under a nitrogen atmosphere to obtain a polymer.

[0168] (Example 1-2) A polymer was obtained in the same manner as in Example 1-1 except that 0.28 parts by mass (0.87 mmol) of CTA4 was used instead of CTA3.

[0169] (Example 2-1) A polymer was obtained in the same manner as in Example 1-1 except that 0.04 parts by mass (0.12 mmol) of CTA3 was used.

[0170] (Example 2-2) A polymer was obtained in the same manner as in Example 1-1 except that 0.01 parts by mass (0.03 mmol) of CTA4 was used instead of CTA3.

[0171] (Comparative Example 1) A polymer was obtained in the same manner as in Example 1-1 except that 0.24 parts by mass (0.87 mmol) of CTA1 was used instead of CTA3.

[0172] (Comparative Example 2) A polymer was obtained in the same manner as in Example 1-1 except that 0.25 parts by mass (0.87 mmol) of CTA2 was used instead of CTA3.

[0173] (Reference Example 1) A polymer was obtained in the same manner as in Example 1-1 except that the chain transfer agent was not used.

[0174] The following evaluation was performed. [Weight average molecular weight (Mw)] The Mw of the polymer was determined by gel permeation chromatography (GPC) under the following conditions. The results are shown in Table 1. ·Measurement device: HLC-8320GPC (manufactured by Tosoh) GPC column configuration: the following 4 columns (1)TSKgel HxL-H (guard column) (2)TSKgel GMHxL (3)TSKgel GMHxL (4)TSKgel G2500HxL Flow rate: 1.0mL / min Column temperature: 40°C · Sample concentration: 1.5% (w / v) (diluted with tetrahydrofuran) Mobile phase solvent: tetrahydrofuran Standard polystyrene conversion

[0175] 〔Polymerization rate〕 The residual monomer amount was measured by the internal standard method using gas chromatography under the following conditions. The residual monomer amount was divided by the amount of butyl acrylate added to the reaction apparatus to calculate the polymerization rate. The results are shown in Table 1. Measuring device: GC-2010Plus (manufactured by Shimadzu Corporation) Chromatographic column: Rxi-5ms 15m, 0.25mmID 0.25μm Column temperature: 50°C Heating program: 50℃(5min)→20℃ / min→250℃(5min) FID temperature: 250℃ Carrier gas: He

[0176]

Table 1

[0177] By comparing Examples 1-1 and 1-2 with Comparative Examples 1 and 2, it is found that when the chain transfer agent of the present invention is used, the molecular weight of the polymer can be effectively controlled. In addition, by comparing Examples 2-1 and 2-2 with Comparative Examples 1 and 2, it is found that when producing polymers of the same molecular weight, the amount of the chain transfer agent of the present invention used is smaller.

[0178] (Second point of view) (Production Example 2-1) In a flask equipped with a stirring device, a nitrogen inlet tube, a thermometer, and a reflux condenser, 100 parts by mass of n-butyl acrylate (BA), 16 parts by mass of a chain transfer agent CTA2-1 having the following structure, and 200 parts by mass of ethyl acetate were added, and the contents of the flask were heated to 70°C while nitrogen was introduced into the flask. Next, 0.1 parts by mass of 2,2'-azobisisobutyronitrile (hereinafter referred to as "AIBN") was added. Heating and cooling were performed for 3 hours so that the temperature of the mixture was maintained at 70°C to obtain a solution containing polymer 1. After the reaction was completed, ethyl acetate was removed from the solution, and polymer 1 was dissolved in tetrahydrofuran (THF) to prepare a solution 1 of polymer 1 / THF=1 mg / mL, and further diluted with a matrix solution (2,5-dihydroxybenzoic acid (DHB) / tetrahydrofuran (THF)=10 mg / mL) to make solution 1:matrix solution=1:10 (mass ratio) to prepare an analytical solution containing polymer 1.

[0179]

Chemistry 25

[0180] <Analysis by MALDI / TOFMS> The polymer solution 1 containing the obtained polymer 1 was analyzed by matrix-assisted laser desorption / ionization tandem time-of-flight mass spectrometry (MALDI / TOFMS) to obtain an MS mass spectrum. The measurement apparatus, measurement conditions, etc. are shown below. Measuring device Device name: ultraflextreme Manufacturer: Bruker Daltonics Inc Measurement conditions Ionization method: Matrix-assisted laser desorption / ionization (MALDI) Ionization mode: positive Mass separation: reflectron mode

[0181] In the MS spectrum of Polymer 1, peaks with the molecular weights shown below were confirmed. Molecular weight = molecular weight of butyl acrylate (128) × n + molecular weight of chain transfer agent CTA2-1 (315) + molecular weight of ionizing agent (Na + or K + )(23 or 39) In the MS spectrum of Polymer 1, peaks corresponding to the molecular weights of integers n = 1 to 33 were confirmed in the above formula. That is, it was confirmed that there are polymer chains having n butyl acrylate monomer units and one chain transfer agent CTA2-1 with a molecular weight. Note that n represents the degree of polymerization of butyl acrylate (the number of repetitions of butyl acrylate monomer units).

[0182] Furthermore, in the MS spectrum of Polymer 1, peaks with the molecular weights shown below were confirmed. Molecular weight = molecular weight of butyl acrylate (128) × n + molecular weight of the part represented by the following formula (26) derived from chain transfer agent CTA2-1 (142) + molecular weight of the terminal structure derived from the initiator (68) + molecular weight of ionizing agent (Na + or K + )(23 or 39) In the MS spectrum of Polymer 1, peaks corresponding to the molecular weights of integers n = 2 to 17 were confirmed in the above formula. That is, it was confirmed that there are polymer chains having n butyl acrylate monomer units, the terminal structure of chain transfer agent CTA2-1 after addition cleavage represented by the following formula (26), and the terminal structure of the initiator represented by the following formula (27). And from this result, it can be seen that chain transfer agent CTA2-1 cleaves to generate a polymer chain having a terminal structure represented by formula (26) and a terminal structure derived from the radical represented by the following (28).

[0183]

Chemical formula 26

[0184]

Chemical formula 27

[0185]

Chemical formula 28

[0186] From the above, in Production Example 2-1, it was confirmed that a polymer chain having a terminal structure represented by the formula (26) derived from the above chain transfer agent CTA2-1 and a terminal structure represented by the formula (27) derived from the initiator was generated. And from this, it can be seen that the polymer chain of the chain transfer agent CTA2-1 having n butyl acrylate monomer units and a molecular weight of 1 molecule is a polymer chain having a terminal structure represented by the formula (26) derived from the above chain transfer agent CTA2-1 and a terminal structure represented by the formula (29) derived from the following chain transfer agent CTA2-1.

[0187]

Chemical Formula 29

[0188] (Production Example 2-2) In Production Example 2-1, the chain transfer agent was changed to a chain transfer agent CTA2-3 having the following structure, and otherwise, a polymer solution 2 containing Polymer 2 was prepared in the same manner as in Production Example 1.

[0189]

Chemical Formula 30

[0190] <Analysis by MALDI / TOFMS> In the same manner as in the polymer solution 1 containing Polymer 1, the polymer solution 2 containing Polymer 2 was analyzed by MALDI / TOFMS to obtain an MS mass spectrum.

[0191] In the MS mass spectrum of Polymer 2, peaks with the following molecular weights were confirmed. Molecular weight = molecular weight of butyl acrylate (128) × n + molecular weight of chain transfer agent CTA2-3 (362) + molecular weight of ionizing agent (Na + or K + ) (23 or 39) In the MS mass spectrum of Polymer 2, peaks corresponding to molecular weights of integers from n = 1 to 33 were confirmed in the above formula. That is, it was confirmed that there exists a polymer chain of the chain transfer agent CTA2-3 having n butyl acrylate monomer units and a molecular weight of 1 molecule. Note that n represents the degree of polymerization of butyl acrylate (the number of repetitions of butyl acrylate monomer units).

[0192] And in the MS mass spectrum of Polymer 2, peaks with the following molecular weights were confirmed. Molecular weight = molecular weight of butyl acrylate (128) × n + molecular weight of the part represented by the following formula (31) derived from chain transfer agent CTA2-3 (189) + molecular weight of the terminal structure derived from the initiator (68) + ionizing agent (Na + or K+ ) molecular weight (23 or 39) In the MS mass spectrum of polymer 2, a peak corresponding to a molecular weight of an integer of n=2 to 17 was confirmed in the above formula. That is, the presence of a polymer chain having n butyl acrylate monomer units, a terminal structure derived from the chain transfer agent CTA2-3 after addition cleavage represented by the following formula (31), and a terminal structure derived from the initiator represented by the above formula (27) was confirmed. And, from this result, it can be seen that the chain transfer agent CTA2-3 is cleaved to generate a polymer chain having a terminal structure represented by formula (31) and a terminal structure derived from a free radical represented by the following formula (32).

[0193] As can be seen from the above, in Production Example 2-2, it was confirmed that a polymer chain having a terminal structure represented by the following formula (31) derived from the chain transfer agent CTA2-3 and a terminal structure represented by the following formula (27) derived from the initiator was generated. Furthermore, from this result, it can be seen that the polymer chain of the chain transfer agent CTA2-3 having n butyl acrylate monomer units and a molecular weight of 1 molecule is a polymer chain having a terminal structure represented by the following formula (31) derived from the chain transfer agent CTA2-3 and a terminal structure represented by the following formula (32) derived from the chain transfer agent CTA2-3.

[0194]

Chemistry 31

[0195]

Chemistry 32

[0196] (Example 2-1) In a flask equipped with a stirring device, a nitrogen inlet tube, a thermometer, and a reflux condenser, 40 parts of n-butyl acrylate (BA), 55.8 parts by mass of 2-ethylhexyl acrylate (2EHA), 4 parts by mass of acrylic acid (AA), 0.2 parts by mass of 2-hydroxyethyl acrylate (2HEA), 0.09 parts by mass of CTA2-1, and 60 parts by mass of ethyl acetate were added, and the contents of the flask were heated to 70°C while introducing nitrogen into the flask. Next, 0.05 parts by mass of AIBN were added to the flask under stirring. Heating and cooling were performed for 2 hours and 30 minutes in a manner that the temperature of the contents in the flask was maintained at 70°C. Next, the temperature was raised to 80°C, and a reflux reaction was performed for 2 hours to obtain a polymer (A-1). After the reaction was completed, the solution was diluted with ethyl acetate to prepare a polymer solution having a solid content concentration of 45% by mass containing the polymer (A-1). The Mw of the obtained (A-1) measured by GPC was 487,000. Furthermore, the corrosiveness was confirmed by the following method.

[0197] <Measurement of weight average molecular weight (Mw)> The weight average molecular weight (Mw) of the obtained polymer was determined by gel permeation chromatography (GPC method) under the following conditions. ·Measurement device: HLC-8320GPC (manufactured by Tosoh) GPC column configuration: The following 4 columns (all made by Tosoh) (1)TSKgel HxL-H (guard column) (2)TSKgel GMHxL (3)TSKgel GMHxL (4)TSKgel G2500HxL Flow rate: 1.0mL / min Column temperature: 40°C · Sample concentration: 1.5% (w / v) (diluted with tetrahydrofuran) Mobile phase solvent: tetrahydrofuran Standard polystyrene conversion

[0198] <Polymerization rate> The amount of residual monomers was measured by the internal standard method using gas chromatography under the following conditions. When calculating the polymerization rate, it was assumed that all monomers other than the monomer measured as the residual monomer participated in the polymerization. The results are shown in Table 1. Measuring device: GC-2010Plus (manufactured by Shimadzu Corporation) Chromatographic column: Rxi-5ms 15m, 0.25mmID 0.25μm Column temperature: 50°C Heating program: 50℃(5min)→20℃ / min→250℃(5min) FID temperature: 250℃ Carrier gas: He

[0199] <Corrosiveness> A polymer solution containing polymer (A-1) was added to a sample bottle, and a copper piece was added. Next, the sample bottle was heated at 150°C for 1 hour to volatilize the solvent in the polymer solution. The sample bottle was sealed, and the copper piece after heating at 150°C for 1 hour was visually checked and evaluated according to the following criteria. 0: No change in the copper sheet (no corrosion) ×: Confirmed that the copper sheet has changed color (corrosive)

[0200] (Examples 2-2, 2-3, Comparative Example 2-1, Reference Examples 2-1, 2-2) The chain transfer agents to be used are shown in Table 1. Except for this, polymers A-2 to A-6 were produced in the same manner as in Example 2-1, and the weight-average molecular weight (Mw), Mw / Mn, and corrosiveness were evaluated. The structures of CTA2-1 and CTA2-3 are as described above, and CTA2-2 has a structure represented by the following formula. Also, n-dodecyl mercaptan (NDM) was used in Comparative Example 2-1, and α-methylstyrene dimer (AMSD) was used in Reference Example 2. The results are shown in Table 1.

[0201] [Chemical Formula 33]

[0202] [Table 2-1]

[0203] (Example 2-4) A polymer solution containing polymer A-1 obtained in Example 2-1 (solid content concentration: 45% by mass), Pencel D-135 (manufactured by Arakawa Chemical Industries, Ltd.) as a tackifying resin, and L-45 (manufactured by Soken Chemical & Engineering Co., Ltd.: isocyanate crosslinking agent) as a crosslinking agent were mixed in amounts such that the solid content ratios were 100 parts by mass of polymer A-1, 20 parts by mass of D-135, and 1.5 parts by mass of L-45, respectively, to obtain an adhesive composition. The adhesive composition obtained above was allowed to stand on a polymethyl methacrylate (PET) film until the bubbles were removed, and then coated with a doctor blade to a dried thickness of 25 μm and dried at 90°C for 3 minutes to remove the solvent and form an adhesive layer. A glass-treated PET film was adhered to the surface on the opposite side of the surface in contact with the PET film of the adhesive layer. Then, it was allowed to age at 40°C / dry for 3 days to produce an adhesive sheet having an adhesive layer with a thickness of 25 μm. The obtained adhesive sheet was evaluated as follows.

[0204] <Adhesive Strength> The adhesive sheet was cut into a size of 25 mm × 150 mm to prepare a test piece. The peeled PET film of the obtained test piece was peeled off, and the exposed adhesive layer was attached to a stainless steel plate (SUS) and pressed back and forth 3 times with a roller weighing 2 kg. After being placed in an atmosphere of 23°C / 50% RH for 2 hours after pressing, the short side of the test piece was pulled in the 180° direction at a peeling speed of 300 mm / min, and the adhesive strength was measured.

[0205] <Retention Force> Cut the adhesive sheet into a size of 20mm×100mm to make a test piece. Peel off the peeled PET film of the obtained test piece, attach the exposed adhesive layer to a stainless steel plate (SUS) to an area of ​​20mm×20mm, and press it back and forth 3 times with a roller weighing 2kg. Then let it stand for 20 minutes in a 40℃ / dry environment, apply a load of 1kg to the shear direction of the test object in the same environment, and measure the displacement of the adhesive layer 1 hour after the start of load application. It should be noted that if it falls less than 1 hour after the start of load application, the time from the start of load application to the fall is recorded.

[0206] <Probe Tack> The adhesive sheet was cut into a size of 20 mm x 150 mm, the PET film after the peeling treatment was peeled off, and the probe tack of the exposed adhesive layer was measured. The probe was 5 mm in diameter SUS, the contact time was 1 second, the probe speed was 1 cm / sec, and the load was 20 g.

[0207] (Examples 2-5 to 2-9, Comparative Examples 2-2, 2-3, Reference Examples 2-3, 2-4) A pressure-sensitive adhesive sheet was produced and evaluated in the same manner as in Example 2-4 except that the type of polymer and the amount of the crosslinking agent used were as shown in Table 2. The results are shown in Table 2.

[0208]

Table 2-2

[0209] (Example 2-10) In a reaction apparatus equipped with a stirring device, a nitrogen inlet tube, a thermometer, and a reflux condenser, 100 parts by mass of isobutyl methacrylate (iBMA), 0.75 parts by mass of partially saponified polyvinyl alcohol as a dispersant, 0.16 parts by mass of CTA2-1, and 200 parts by mass of ion exchange water were added, and the contents of the flask were heated to 70°C while introducing nitrogen into the flask. Next, 1.5 parts by mass of lauroyl peroxide was added to the stirred flask, and after a polymerization reaction for 4 hours, the reaction system was cooled to obtain a dispersion of polymer particles 10. The obtained dispersion of polymer particles 10 was filtered and then dried to obtain polymer particles 10. The obtained polymer particles and dispersion were evaluated by the following method. The Mw of polymer particles 10 was 164,000 and the particle size was 238 μm. The method for measuring the weight average molecular weight (Mw) and Mw / Mn was the same as that of Example 2-1.

[0210] <Polymerization rate (iBMA residual amount in dispersion)> The iBMA residual amount (ppm) in the dispersion obtained in the example (polymerization liquid after the polymerization reaction) was measured by gas chromatography, and the polymerization rate was calculated. The measurement conditions of the gas chromatography were as described above.

[0211] <Particle size> 2 g of polymer particles 10 were placed on a slide glass and covered with a cover glass. The cover glass was observed from above using a microscope (VHX-5000: manufactured by Keyence). Figure 1 as well as Figure 2 ). The polymer particles 10 are almost spherical. The particle diameters of 10 random polymer particles are measured from the obtained observation image, and the average particle diameter is calculated.

[0212] <Corrosiveness> After adding 3 g of polymer particles 10 to the sample bottle, 5 g of ethyl acetate was added to dissolve the polymer particles 10. A copper piece was added to the sample bottle and heated at 150° C. for 1 hour to volatilize the ethyl acetate. The sample bottle was sealed, and the copper piece after heating at 150° C. for 1 hour was visually checked and evaluated according to the following criteria. 0: No change in the copper sheet (no corrosion) ×: Confirmed that the copper sheet has changed color (corrosive)

[0213] (Examples 2-11 to 2-13, Comparative Example 2-4, Reference Examples 2-5 and 2-6) Except that the kind and amount of the chain transfer agent used were as shown in Table 3, a polymer was produced and evaluated in the same manner as in Example 2-10.

[0214]

Table 2-3

[0215] As can be seen from the above, the polymer of the present invention is less likely to cause corrosion and reduced adhesive properties. Furthermore, according to the production method of the present invention, the molecular weight can be controlled at a sufficient polymerization rate regardless of the type of radical polymerizable compound to be polymerized.

Claims

1. A chain transfer agent represented by the following formula (1): In formula (1), X is selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , and OR 1 Y and Z are selected from cyano, arbitrarily substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , OR 1 、OC(O)R 1 、N(H)C(O)R 1 and a halogen group, or an arbitrarily substituted carbocyclic structure or an arbitrarily substituted heterocyclic structure formed by bonding Y and Z, X, Y, and Z are the same or different, and R 1 is a group optionally substituted with an alkyl group having 1 to 8 carbon atoms, Q is hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group, R 2 and R 3 is a group selected from hydrogen, an alkyl group having 2 to 6 carbon atoms, an optionally substituted aryl group, and an optionally substituted heterocyclic structure, R 2 With R 3 Same or different, but excluding R 2 With R 3 All are hydrogen cases.

2. The chain transfer agent according to claim 1, wherein The R 2 and R 3 At least one of them is hydrogen.

3. The chain transfer agent according to claim 1, wherein The R 2 and R 3 At least one of them is a group selected from an optionally substituted aryl group and an optionally substituted heterocyclic structure.

4. The chain transfer agent according to claim 1, wherein The chain transfer agent is composed of a skeleton represented by formula (23), In formula (23), R 21 , R 22 , R 23 , R 24 , and R 25 is a group selected from hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, a carboxyl group, and a halogen group, and R 21 , R 22 , R 23 , R 24 , and R 25 Same or different, X is selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , and OR 1 The group, R 1 is a group optionally substituted with an alkyl group having 1 to 8 carbon atoms, R 51 and R 52 is an alkyl group having 1 to 8 carbon atoms, R 51 and R 52 The same or different, R 6 It is hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group.

5. A method for producing a polymer, The method comprises the step of polymerizing a radical polymerizable compound in the presence of the chain transfer agent according to claim 1 or claim 4.

6. The manufacturing method according to claim 5, In the polymerization step, the radical polymerizable compound is polymerized in one or more organic solvents selected from the group consisting of ethyl acetate, ethyl methyl ketone, and toluene.

7. A method for producing an adhesive composition, comprising a polymer production step and a crosslinking agent mixing step, In the polymer production step, the polymer is produced by the polymer production method according to claim 6, In the crosslinking agent mixing step, at least one crosslinking agent selected from an isocyanate crosslinking agent, an epoxy crosslinking agent, and a metal chelate crosslinking agent is mixed with the obtained polymer.

8. The manufacturing method according to claim 5, In the polymerization step, the radical polymerizable compound is polymerized in an aqueous medium.

9. A polymer comprising a polymer chain having a group represented by the following formula (18) at the terminal, In formula (18), X is selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , and OR 1 The group, R 1 is a group optionally substituted with an alkyl group having 1 to 8 carbon atoms, R 2 and R 3 is a group selected from hydrogen, an alkyl group having 2 to 6 carbon atoms, an optionally substituted aryl group, and an optionally substituted heterocyclic structure, R 2 and R 3 Same or different, but excluding R 2 With R 3 All are hydrogen cases.

10. The polymer according to claim 9, wherein The group represented by the formula (18) is represented by the following formula (21), In formula (21), R 21 , R 22 , R 23 , R 24 , and R 25 is a group selected from hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, a carboxyl group, and a halogen group, and R 21 , R 22 , R 23 , R 24 , and R 25 The same or different, X is selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , and OR 1 The group, R 1 It is a group optionally substituted by an alkyl group having 1 to 8 carbon atoms.

11. The polymer according to claim 9 or claim 10, wherein The polymer chain having a group represented by the formula (18) at the terminal further has a group represented by the following formula (19) at the terminal, Y and Z are each selected from cyano, optionally substituted aryl, acyl, carboxyl, COOR 1 、C(O)NH2、C(O)NHR 1 、C(O)NR 1 2. SOR 1 、SO2R 1 、SO3R 1 , OR 1 、OC(O)R 1 、N(H)C(O)R 1 and a halogen group, or Y and Z bond to form an arbitrarily substituted carbocyclic structure or an arbitrarily substituted heterocyclic structure, Y and Z are the same or different, R 1 is a group optionally substituted with an alkyl group having 1 to 8 carbon atoms, Q is hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group.

12. The polymer according to claim 11, wherein The group represented by the formula (19) is represented by the following formula (22), In formula (22), R 51 and R 52 is an alkyl group having 1 to 8 carbon atoms, R 51 and R 52 The same or different, R 6 It is hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group.

13. The polymer according to claim 9 or claim 10, wherein The sulfur content of the polymer derived from the mercaptan chain transfer agent is 100 ppm or less.

14. The polymer according to claim 9 or claim 10, wherein The polymer chain has repeating monomer units, The repeating monomer unit has at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, and an amide group.

15. An adhesive composition comprising The polymer according to claim 14, and At least one crosslinking agent selected from the group consisting of isocyanate crosslinking agents, epoxy crosslinking agents, and metal chelate crosslinking agents.

16. A polymer particle comprising the polymer according to claim 9 or claim 10, The average particle size of the polymer particles is 0.05 to 500 μm.

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