TW201247721A - (meth)acrylic ester copolymer, adhesive composition containing it, and manufacturing method of (meth)acrylic ester copolymer - Google Patents

Abstract

The present invent provides a (meth)acrylic ester copolymer having a alkoxy amine skeleton in its side chain, which is a novel (meth)acrylic acid-based copolymer capable of greatly controlling a cross-linking reaction. The (meth)acrylic ester copolymer can be formed by structural units represented by following formula (I).

Description

201247721, OBJECTS OF THE INVENTION: Field of the Invention The present invention relates to a (mercapto) acrylate copolymer and a composition comprising the same, and a (meth) acrylate copolymer. Second, in other words, a (meth) propylene = copolymer having an amphetamine skeleton in a side chain. [Prior Art] Various proposals have been made to use the acrylic acid-based copolymer, and it has been put into practical use. An example of such an acrylic adhesive is an adhesive which uses an acrylic acid copolymer obtained by a parent-linked reaction of a heterogeneous compound and a monomer having a trans group. Things. In general, the polymer is composed of a strong bond called a covalent bond, so that the polymeric reflective structure is fixed, unless it is a special condition, that is, the molecular structure. However, if a special co-existence (secret covalent bond) which is cracked by heat or contact with the stimulus is introduced into the polymer, a polymer that freely controls the structural change can be constructed. In the non-patent document 1 towel, as a polymer capable of controlling the change of the structure, there is a dynamic covalent relationship between the second sister and the oxidized amine system which leads to the skeleton of the so-called "homoxamine" in the main chain of the polymer. The molecule of the bond has a 2 k at room temperature, but (4) the part that heats the 'bonding' will reversibly dissociate / twentieth, as described in Non-Patent Document 1, synthesizing the oxoamine skeleton in the main chain. , Amino decanoic acid § | 'The exchange reaction based on the oxy-amine skeleton is carried out in two kinds, and the recombination is carried out to form a composite with a complex and complex polymer. [Previous Technical Literature] 4/25 201247721 [Non-Patent Literature Non-Patent Document 1 "Polymer Scrambling: Macromolecular Radical Crossover Reaction between the Main Chains of Alkoxyamine-Based Dynamic Covalent Polymers", Journal of the American Chemical Society, Vol. 125, pp. 4064-4065, 2003 [Summary of the Invention] OBJECTS TO BE SOLVED BY THE INVENTION The isocyanate compound is highly reactive with water in the warp or air, so it is difficult to control the conventional adhesive using an acrylate and an isocyanate copolymer. Linking reaction, but there is a problem of coatability or the case where adhesive residue is generated of. Thus, the present invention is intended to provide a novel acrylic copolymer capable of highly controlling the crosslinking reaction. [Means for Solving the Problems] In order to solve the above problems, the present invention provides a (fluorenyl) acrylate copolymer having an alkoxyamine skeleton in its side chain. The (mercapto) acrylate copolymer, upon heating, forms an exchange structure between the molecular chains based on an exchange reaction of an alkoxyamine skeleton. The crosslinked structure is reversibly formed and dissociated, and the (fluorenyl) acrylate copolymer of the present invention is subjected to reaction conditions such as temperature and time adjustment, and the cross-linked structure of the ruthenium (meth) acrylate copolymer is obtained. , arbitrarily control the degree of crosslinking. The (meth) acrylate copolymer of the present invention may be one formed by the structural unit represented by the following general formula (1). 5/25 201247721

In the formula (1), R] represents a linear or branched alkyl group having 4 to 8 carbon atoms. The heart ~K represents a hydrogen atom or a sulfhydryl group, respectively. The ruler 2 to the heart can be the same or different. R5 represents a hydrogen atom, an oxygen atom, a hydroxyl group, or a carbon atom! A straight chain of ~8 or a branched alkyl group, an alkoxy group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms. The alkyl group and the alkoxy group may have one or more oxygen atoms, sulfur atoms, carbonyl groups, ester groups, decylamino groups or imine groups in the chain. In the above general formula (1), the copolymerization ratio Y: Z is 0.5: 1 to 2: 1, and the copolymerization ratio X: Y or X: Z is preferably 15: 1 to 25:]. Further, the present invention also provides an adhesive composition comprising the above (meth) acrylate copolymer. The adhesive composition is heated to change the parent structure of the molecular chain formed by the (meth) acrylate copolymer based on the exchange reaction of the oxygenated amine skeleton, whereby the physical properties as an adhesive can be controlled. In addition, the present invention also provides a method for producing a copolymer of a copolymer of acrylates, wherein the side chain has an amphetamine skeleton, which comprises a step of copolymerizing an acrylate monomer mixture, and the copolymerized acrylate monomer The mixture includes an acrylate monomer having an alkoxyamine skeleton. In the production method, the aforementioned step may be a (meth) acrylate monomer represented by the following general formula (II), and the following general formula (III) And the following 6/25 201247721 step of copolymerization of a (fluorenyl) acrylate monomer having an oxy-amine skeleton which is not in the general formula (IV).

Ph one ( \ r4 =(' )=〇 〇· \

Ph—/

b. In the formula (ιν) / in the formula (II), R! represents a linear or branched alkyl group having 4 to 8 carbon atoms. In the formulae (II) to (IV), R2 to R4 each represent a hydrogen atom or a fluorenyl group. R2 to R4 may be the same or different. In the formula (IV), R5 represents a hydrogen atom, an oxygen atom, a hydroxyl group, a linear or branched alkyl group having a carbon number of 7/25 201247721 1 to 8, alkoxy group having a carbon number of 丨8 or a carbon atom. 5 8 ring yard base. The above-mentioned alkyl group and the above alkoxy group may have one or more oxygen atoms, sulfur atoms, carbonyl groups, ester groups, decylamino groups or imine groups in the bond. In the foregoing step, the (mercapto) propionic acid styrene having an alkoxyamine skeleton represented by the above general formula (III) and the (meth)acrylic acid having a oxime amine skeleton represented by the above formula (IV) The copolymerization of the g-specific monomer is preferably set to 〇·5: 卜2: the sulfonyl acrylate monomer represented by the formula (II) is generally as described in the foregoing 11) or (IV). The copolymerization of the (meth)acrylic acid acrylate monomer having an aerobic amine skeleton is preferably set to 15:1 to 25:1. Further, as the polymerization initiator in the above step, 2,2,-azobisdecyloxy-2,4-dicinyl valeronitrile is preferably used. In the present invention, "(indenyl)acrylic acid" means acrylic acid and methacrylic acid. [Effect of the Invention] A novel bismuth acrylate copolymer which can highly control the crosslinking reaction can be provided by the present invention. [Embodiment] [Embodiment of the Invention] Hereinafter, a preferred embodiment of the present invention will be described with reference to the "8". The following is a description of the embodiments of the present invention, and is not intended to limit the scope of the present invention. i (Meth) acrylate copolymer The (fl:) propyl group of the present invention has a (b) a oxy-amine skeleton having a valence bond in the side chain. The (meth)acrylic acid vinegar copolymer can be produced via a mixture of ocyanate 8/25 201247721 enoate monomers, and the acrylate monomer mixture comprises an acrylate monomer having an alkoxyamine skeleton. A suitable embodiment of the (mercapto)acrylic acid s-ruthenium copolymer of the present invention may be one formed from the structural unit represented by the following general formula (I).

In the formula (I), R represents a linear or branched alkyl group having 4 to 8 carbon atoms. R2 to r4 each represent a hydrogen atom or a methyl group. I, which may be the same or a hydrogen atom, an oxygen atom, a transradical group, a carbon atom or a straight chain or a branch, a group having a carbon number of 丨8 or 8 or a ring having a carbon number of 5 to 8 earth. W-Wei-based and pre-Wei-oxyl can also be contained in the chain towel, sulphur, county, _ base or sub-county. In other words, the former secret group and the former base are interrupted by an oxygen atom, a sulfur atom, a hetero group, an i group, a hetero group or an imine group. 'Top type (1) towel '7 oxamine skeleton _ through the key to the bond = C contact material chain, spider oxygen when the main chain key: and not limited to (four) key, can also be for example silk key or Lai, relieve this The (meth)acrylic acid-g-copolymer of the invention can be pulverized via a general acid of the following general formula, and has a 6-oxoamine skeleton with the following general formula _ and the following: Base) C riding from the purpose of a total of 9/25 201247721 polymerization to manufacture.

Ri

•. (m)

Ph—~,

• · · (汉) The r丨~R5 in the formulas (H) to (IV) are the same as the R丨~heart in the formula (I). A suitable example of the (meth) acrylate copolymer formed by the structural unit represented by the formula (1) is a (meth) acrylate copolymer formed by the structural unit represented by the following formula (la). . The (meth)(tetra)acid i-copolymer corresponds to the above formula (1), and R] is 10/25 201247721 2 ethylhexyl group, and I to I are a hydrogen atom and a methoxy group. The (meth) acrylate vinegar copolymer composed of the structural unit represented by the formula (la) can be obtained by using a (meth)acrylic acid 2-ethylhexanoic acid monomer, and having the following formula (nia) = The (meth) acetoacetate monomer 2 tu having the aerobic amine skeleton represented by the formula (IVa) is produced. Hereinafter, the (meth)acrylic acid 2-ethylhexyl vinegar monomer is sometimes referred to as "2EHA", and the (meth)acrylic acid having the oxime amine column shown by the formula (IIIa) and the formula (IVa) is used. The ester monomers are referred to as "ALA "ALA2", respectively.

The oxy-amine is heated and the part of the bond is reversibly dissociated and added. Thus, the (mercapto)acrylic acid vinegar copolymer of the present invention is heated, i.e., based on the exchange reaction of the oxirane, in a molecular _-shaped hybrid structure. In Fig. 1, a cross-linking reaction of a fluorenyl-acrylic acid vinegar copolymer composed of a structural unit represented by the above general formula (Ia) is exemplified as an example. . After heating, the oxygen atoms in the oxygen-containing saddle skeleton of ALA1 and ALA2 and the carbon bond bonded to the oxygen atom are solved, although the part of the AA1 and ALA2 oxirane skeletons of the copolymer backbone is dissociated from each other. Bonding again produces a low molecular weight alkoxyamine. The surface is still bonded to the remainder of the co-aged ALA1 and ALA2 oxygen (four) frames, and a crosslinked structure is formed between the main chains. Since the crosslinked structure can be reversibly formed and dissociated, the degree of crosslinking can be arbitrarily controlled by changing the structure of the (meth)acrylic acid § copolymer by temperature and time. 9 The cross-linking reaction can be carried out under an insoluble ship (block system). The reaction temperature can be set, for example, to 60 to 160 °C. The reaction time is, for example, 12 to 48 small; 'dish: 2 2 21 hours' is more preferably 3 to 12 hours, and sometimes it may be several minutes to tens of times. Further, the solvent-free condition is a condition in which the solvent concentration is not more than 10 ppm unless it is substantially free of a solution. /, Further, the degree of crosslinking of the copolymer obtained by the cross-linking reaction can be arbitrarily controlled by adjusting the amount of introduction of the oxamine skeleton (that is, the polymerization rate with respect to the ship ALA1 and ALA2). .

2EHA and ALA1 copolymerization ratio (X 2EHA^ ALA2 一般 in the general formula (1): ι ratio σ··z) ==:1 〜2〇:1. And the copolymerization of ALA1 and ALA2 丨~2: The material of the material for ALA1 and _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Another =:: The temperature of the glass transition of the copolymer is lowered, so that the adhesion of the (meth) thief of the invention is dilute vinegar (four) material _ Na temperature 赖 point = (=): 12 /25 201247721

The glass transition temperature of the 2EHA-Tanbenfa 3 (mercapto)-acrylic copolymer is preferably in the range of *2 °C or less. Further, the glass transition temperature of poly(2-ethylhexyl acrylate) was -70. (: Left and right. 匕) The acrylate monomer used in addition to jEHA may be a monomer having a glass transition temperature of 2 〇〇C or less, such as butyl acrylate or 2, hydroxyethyl acrylate. The glass transition temperature can also be arbitrarily adjusted by adjusting the copolymerization ratio of ALA1 and AW, and to the monomer of (1). (4) Giving (the no matter of the Lanna temperature of the product), propylene--日早虹The copolymerization is preferably in the above range. 2. Adhesive composition (Methyl) acrylic acid vinegar copolymer can be formed in the distribution of the solvent-free HI-based oxy-amine skeleton exchange as described above. Therefore, if the (meth)acrylic acid®1 copolymer is screamed for the towel, it is difficult to control the adhesive composition by changing the cross-linking structure between the two sub-chains of the exchange reaction. Material modification, __g|filaments =; viscosity, adhesion, elasticity of the adhesive composition, heat resistance, and resistance to the 可 Γ Γ can be used for various processes, particularly useful for the composition of the composition due to burning oxygen before heating The amine skeleton is not deformed' but after heating, it is based on the cross-linking and reaction of the aerobic amine skeleton. "The cross-linking structure is formed between the sub-chains, so agglutination occurs. Thus, 13/25 201247721 can be easily and fully coated with the transfer agent by using the transfer agent of the present invention. Then, after heating, the adhesive surface can be easily self-transferred. This adhesive agent can, for example, threaten the adhesion of the adhesive sheet formed by the manufacturing step of the electric component. Moreover, the acrylic acid s of the present invention is intended to be silky. In addition to the (4) composition, it can also be applied to a church material, a coating agent, a printing ink, etc. 3. A method for producing a (meth) acrylate copolymer is taken from the production of a (meth)acrylic acid S copolymer. The method comprises the steps of: co-human: a mixture of two dilute ga monomers, and the propylene monomer mixture 3 has an acrylate monomer having an alkoxyamine skeleton. The appropriate embodiment of the January | J逑 step can be In order to copolymerize an acrylic acid acrylate monomer having the following general formula (9), and a general formula (ΠΙ) having the following formula (ΠΙ) and the following generally shown as an oxygen-reducing amine

Ph • (nr)

14/25 201247721 r4 ,=:Ο O' \

Ph—/

In the formulae (II) to (IV), R1 to R5 are the same as those in the formula (I). Here, in the above formula (III)' (Ιν), the hexaamine skeleton is bonded by vinegar bonds. The main chain of the (meth)acrylic acid g-copolymer, but the bond between the pyrogalline skeleton and the main chain is not limited to the g-key, and may be, for example, silk. _ key or 趟 key, guanamine bond, etc. The (mercapto)propyl copolymer (10) of the present invention is produced by copolymerizing these (indenyl) (10) acid g monomers, and each monomer is dissolved in a solvent together with a polymerization initiator, and it is necessary to add The silk is subjected to a free silking reaction. As the solvent, for example, toluene, ethyl acetate, methyl ethyl ketone, acetone or the like can be used. The copolymerization of the acid-specific monomer mixture can also be carried out in the absence of a solvent. The reaction temperature is preferably less than 6 〇 QC. The reaction time is not particularly limited and may be set, for example, within 48 hours. As the polymerization initiator, in order to secure the thermal stability of the alkoxyamine, a low-temperature polymerization initiator is preferably used. As a low-temperature polymerization initiator, as long as the cross-linking reaction temperature of a soil i (mercapto)-propionic acid-copolymer (based on the oxygenated amine X ^ six parental reaction '60~160 C), the temperature can be effective. No special yang can be used, for example, 2,2 azobis(4-decyloxy-2,4_dimethyl 戍 guess

Azobis(4-methoxy-2.4-dimethylvaler〇nitrile^ ' 9 ' , 5/25 仏 仏 双 2012 201247721 崎 The paste is further oxidized by the principle H-side (methyl) propyl fine monomer, and with the above formula The copolymerization ratio of the monomer (X in the core formula (I) in the general formula®: the copolymerization ratio of the base monomer (generally 4 m, / (meth) acrylate monomer represented by the above formula (ΙΠ)共聚 The copolymerization ratio of G.5=(meth)acrylic acid _ can be synthesized by the monomer reaction of acryl:::methyl)acrylic acid acetate to synthesize the alcohol derivative of octa- oxamine The condensed Example <Example 1> The oxyalkylamine propylene oxime monomer (ALA1 and ALA2) ester monomer (αΓαΤ乳μ amine was synthesized in one step to synthesize a acetaminophen-based group containing a burnt-oxygen skeleton. ^>2,2,6,6:. 6.〇_〇1), then two § ' 5.〇_〇1) and triethylamine (〇, 吣, adding propylene I to the chamber fluid) Chlorine (4), dry and solid. Mix with milk for 16 hours. Then steam the layer. Separate the residue by evaporation of chlorine. Wash the water with dichloromethane. Dry it with acid and dry it.曰 烧 ( (m, ν / ν)., the crude product was added to the rapid chromatography plus 16 / 25 201247721 Acrylate (ALA1) was prepared by 'analysis, refining, and obtained colorless viscous oil (23 g, yield 74%) under vacuum to obtain acrylate (ALA1). Proton NMR spectrometry was performed using Bruker ( The 400 MH z ) spectroscope 'is carried out at 4 ° C with tetrakisyl sulphur (TMS) as the internal standard by hydrazine (CDCl3). iH-NMR (4 Hz, CDC13): delta/ppm 0.69 (s, (3, CH3) , 4.80 (q, 1H, CH), 5.11 (m, 1H, CH), 5.81 (d, 1H, vinyl proton), 6.19 (q, 1H, vinyl proton), (d, 1H, vinyl proton), 7.23- 7.39 (m, 5H, aromatic proton). In a dry tetrahydrofuran (4 ml) was added 4-decyloxy-indole 2,-transyl-1,-phenethyl)oxy)·2,2,6,6· Tetramethyl piperidine (1.54g, 5.〇mmo丨) and triethylamine (〇.6g '6.0mm〇1), and then added propylene chloride (0.54g '6.0mm〇i) to the formed solution Stir at room temperature under nitrogen for 16 hours. It is then evaporated to dryness. The evaporation residue was separated by water and dioxane. Wash the water layer with dioxane. The organic layer with the cleaning solution is dried with magnesium sulfate and evaporated to dryness. The crude product was dissolved and purified by flash chromatography using ethyl acetate/hexane (1/1, v/v). The obtained colorless viscous oil (1.72 g, yield 95%) was dried under vacuum. Solid's acrylate (ALA2). , iH-NMR (400 Hz, CDC13): delta/ppm 0.71 (s 3HCH,) 1.11 (s, 3H, CH3), 1.26 (s, 3H, CH3), 1.41 (s, 3H, ch3), 168· 2.03 (dd,2H, CH2), 3.32(s,3H,CH3), 3.43 (m, 1H, CH)'' 4 26_ 5.02 (m, 2H, CH2), 4.69 (q, 1H, CH), 5.78 (d , 13⁄4 vinyl proton), 6.06 (q> 1H? vinyl proton), 6.33 (d, 1H, vinyl pr〇t〇n)? 17/25 201247721 7.24-7.41 (m, 5H, aromatic proton). Polymerizable acrylic acid Both the component and the alkoxyamine component were confirmed by nmr spectroscopy (Fig. 2). Its system shows that ALAI synthesis is successful. Further, as shown by the ALA2 NMR spectrum of Fig. 3, all of the peaks were directed to an acrylic component and an alkoxyamine component. (2) Synthesis of low Tg polymer low Tg polymer with alkoxyamine skeleton, consisting of 2EHA and acrylate monomer containing two kinds of aerobic amines (ALA1 and ALA2), with molar ratio (2EHA: ALAI : ALA2) 18 : 1: 1 is formed by copolymerization. The free radical copolymerization is carried out in toluene at 40 °C in the presence of the initiator 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile) [ν-70]. 18 hours (23% conversion rate of 2EHA, yield 83%). 2EHA (1.66 g, 9 mmol), ALAl (0.17 g, 0.5 mmol), ALA2 (0.18 g, 0.5 mmol), and toluene (2 ml) were placed in a round bottom flask placed in a magnetic stirrer under an argon atmosphere. The initiator V-70 (0.1542 g, 0.475 mmol) was added. The viscous product was washed with methanol to give poly(2EHA_c〇·ALA1-C0-ALa2) (i.66 g, yield 83%, Mn = 22000, Mw/Mn = 3.33). The structure of the obtained polymer was determined by the 2 NMR spectrum shown in Fig. 4. Since the low temperature initiator V-70 was used in the polymerization, no decomposition of the alkoxyamine was observed. The molar ratio of 2EHA, ALA, and ALA2 of the obtained polymer was calculated from the peak area, and the calculated lanthanide ratio was matched with the monomer input ratio. These results show that poly(2£-〇〇-八1^1-〇〇-八1^2) is obtained by random copolymerization of 2EHA with ALA1 and ALA2. Figure 5 shows molecular sieve chromatography of poly(2EHA-co-ALAl-co-ALA2) 18/25 201247721 (SEC). The number average molecular weight (Mn) was 22,000, and the polydispersity index (Mw/Mn) was 3.33. ^ Determined by gel permeation chromatography (GPC) at 40. (:, under the TOSOH TSK guard column Super HL, 3 kinds of columns (TOSOH TSK gel super Η 6000, 4000, 2500) and UV/visible light detector TOSOH HLC-8220 GPC system. The precipitation agent used THF (0.6 ml/min). The calculation of the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the polymer was carried out using a polystyrene standard for calibration (]^=1,060-1, 〇90, 〇〇〇

Mw/Mn = 1.02-1.08). In order to analyze the thermal characteristics of poly(2EHA-co-ALAl-co-ALA2), it was measured by differential scanning calorimetry (DSC). The DSC was measured using EXSTAR6000 (Seiko Instruments Co., Ltd.) at a heating rate of ιοκ/min in a temperature range of 153 to 323K. The results are shown in Figure 6. The poly(2£11 八气〇-八1^14〇-八1^2) § is estimated to be -48 ° C, which is a low Tg polymer classification higher than the Tg (-70 〇 C) of P2Eha. σ (3) Crosslinking reaction of low Tg polymer The crosslinking reaction of the low Tg polymer was carried out under a block condition at 24 ° C for 1 hour. The poly(2EHA_co_ALA: Uc〇_ALA2X〇.1〇g, Mn = 22000 Å Mw/Mn = 3.33) was subjected to a freeze-decompression-dissolution cycle, degassed in a glass tube, and sealed under vacuum. Further, the glass tube was heated at 1 C C3 for 24 hours to obtain a crosslinked polymer. Heating such as a polymer can flow at room temperature (refer to Fig. 7 (a)). On the other hand, the polymer after heating is gelatinized (see Fig. 7(b)). 19/25 201247721 In order to prove that the crosslinking reaction was carried out, the heated polymer was placed in a clump of ether. Phenyl oxime ether can dissolve poly(2£11-8-(;〇-八]^1<〇-八1^2). Figure 8(4) shows that the heated poly(2EHA-co-ALA1 -co-ALA2) is added. Photograph of the front of the alum ether, and Figure 8(b) shows the photo of the heated poly(2EHA-CO-ALA1-CO-ALA2) after 48 hours of addition to the phenyl ether. The heated poly(2EHA-co -ALAl-co-ALA2) is insoluble in benzoin and is swelled into a gel. This is a characteristic behavior of the crosslinked polymer, and it was confirmed that the crosslinking reaction was carried out. In order to further confirm the progress of the crosslinking reaction, Therefore, the reaction by-product 4-decyloxy-1 ((2'-trans)·1,-phenethyl)oxy>2,2,6,6-tetradecylpiperidine was analyzed. After heating by NMR measurement The poly(2EHA, ALA1_c〇_ALA2) was dissolved in the benzene test. The NMR spectrum is shown in Figure 9. In addition to the translation of the insufficiently soluble soluble polymer, it was clearly observed that the ALA1 unit and the ALA2 unit were produced. The formation of oxamine by-products in the hospital. It is confirmed that a crosslinking reaction occurs between the ALAl unit and the ALA2 unit. 〆, [Industrial Applicability] The present invention can be used as an adhesive. Γΐ Γΐ Γΐ Γΐ ( (4) oil ^. _ Yes (4) The adhesive group can be used as a kind of adhesive surface which can be adhered to the surface of the adhesive before being heated, and can be used for forming, for example, to form: The adhesive layer of the splicing sheet used in the step of [4] The following is a schematic diagram for explaining the cross-linking of the (meth)(10) acrylate copolymer of the present invention 20/25 201247721 Fig. 2 is a graph showing the NMR spectrum of ALAI Fig. 3 is a graph showing the NMR spectrum of ALA2 Fig. 4 is a graph showing the NMR spectrum of poly(2EHA-co-ALAl-co-ALA2). Molecular sieve percolation chromatography (SEC) chromatogram of poly(2EHA-co-ALAl-co-ALA2) Figure 6 is a differential scanning calorimetry (DSC) heat showing poly(2EHA-co-ALAl-co-ALA2) Figure 7 (a) and (b) are photographs showing pre-heating (8) and post-b (b) of poly(2EHA-CO-ALA1-CO-ALA2). Figures 8(8) and (b) show the heating The photo of the pre-swelling 0) and the post- (b) of the poly (2EHA_c〇_ALa丨_c〇-ALA2). The picture shows, the, and the page shows the dissolved poly (2eha_co_ al A1 -CO-AL A2) dissolved. A chart of the NMR spectrum of the singularity. Main component symbol description] Benefits 21/25

Claims (1)

201247721 VII. Patent Application Range: 1. A (mercapto) acrylate copolymer having an alkoxyamine skeleton in a side chain. 2. The (mercapto) acrylate copolymer of claim 1 which is constituted by the structural unit represented by the following general formula (I): In the formula (1), Ri represents a linear or branched alkyl group having 4 to 8 carbon atoms; R2 to R4 each independently represent a hydrogen atom or a methyl group; and Κ·4 may be the same or different; Κ·5 represents a hydrogen atom and oxygen. Atom, a meridine, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms; the aforementioned alkyl group and the aforementioned alkoxy group There may also be more than one oxygen atom, sulfur atom, carbonyl group, ester group, guanamine group or imine group in the chain. 3. The (mercapto) acrylate copolymer according to claim 2, wherein in the above general formula (I), the copolymerization ratio Y: Ζ is 0.5:1 to 2: 1, copolymerization ratio: Υ or Χ :Ζ15: 1~25: 1. An adhesive composition comprising the (mercapto) acrylate copolymer according to any one of claims 1 to 3. 5. A method for producing a (fluorenyl) acrylate copolymer having an alkoxyamine skeleton in a side chain, which comprises a step of copolymerizing an acrylate monomer mixture, step 22/25 201247721, the acrylate monomer mixture comprising An acrylate monomer having an alkoxyamine skeleton. 6. The method for producing a (fluorenyl) acrylate copolymer having an alkoxyamine skeleton in a side chain according to the fifth aspect of the patent application, wherein the aforementioned step is a sulfhydryl group represented by the following general formula (Π) The step of copolymerizing an acrylate monomer with a (fluorenyl) acrylate monomer having an alkoxyamine skeleton represented by the following general formula (III) and the following general formula (IV): ••式(π) Ph—< 23/25 201247721 r4 o Formula (IV) In the formula (8), 'R】 represents a linear formula of (4) to (IV) t having a carbon number of 4 to g, and R2 to R4 are classified as a group of bases, and R4 may be the same or different; fly poor or methyl; & (IV) 'R5 represents a hydrogen atom, an oxygen atom, a linear or branched quinone of -8, a carbon number of 1 atomic number 5~ 8 cut, silk; pre-Wei pre-Wei may also have good oxygen on -_, sulfur atom T group in the chain amine or imine group. Sulfhydryl, ester group, oxime 7. Ph-^ = a method for producing a copolymer of acetaminophen in the side chain of the acetaminophen skeleton in the side chain of the patent application, wherein in the foregoing step (the lanthanide series will be represented by the above general formula (111) The copolymerization ratio of the alkoxylated acid s-type monomer having an alkoxyamine to the oxime amine skeleton 2 (meth) acrylate monomer represented by the above formula (5) is set to 〇.5 : ” Upper Z * 1 Further, the (mercapto) acrylate monomer represented by the above general formula (II) and the copolymer of the oxime acrylate monomer having the alkoxyamine skeleton represented by the above general formula (III) or formula (IV) The ratio is set to 15: 1 to 25: 1. The method for producing a (fluorenyl) acrylate copolymer having an alkoxyamine skeleton in a side chain according to any one of claims 5 to 7, wherein the first 24 /25 8. 201247721 The procedure described is the use of 2,2'-azobis(4-mercapto-2,4-didecyl valeronitrile) as a polymerization initiator. A method of structurally heating a (mercapto) acrylate copolymer having an alkoxyamine skeleton in a side chain at a solvent concentration of 1 〇〇〇 ppm or less, based on an alkoxyamine bone Exchange reaction to change the crosslinked structure formed between the molecular chains. - A method for controlling the physical properties of the adhesive composition, which is formed by a (fluorenyl) acrylate copolymer having an alkoxyamine skeleton in a side chain. The adhesive composition is heated to change the parent structure formed between the molecular chains based on the exchange reaction of the aerobic amine skeleton, thereby controlling the physical properties of the adhesive composition. 25/25