JP4468134B2 - (Meth) acrylate polymer - Google Patents

Description

  The present invention relates to a (meth) acrylate polymer and a production method thereof, and a terminal hydroxyl group-containing compound useful as a production intermediate of the (meth) acrylate polymer and a production method thereof. The (meth) acrylate polymer is a compound useful for, for example, a pressure-sensitive adhesive or adhesive for various substrates.

  In recent years, various types of curable resin compositions have been developed.For example, as an adhesive composition that instantly cures by irradiating an electron beam and gives an adhesive layer having both high adhesive strength and flexibility, An electron beam curable adhesive composition for laminating comprising at least one selected from the group consisting of (meth) acrylic acid and carboxyl group-containing mono (meth) acrylate and polyurethane poly (meth) acrylate has been proposed. (For example, refer to Patent Document 1).

  However, since the curable adhesive composition is inferior in holding power to a substrate such as metal, for example, development of a compound that can be suitably used for an adhesive composition with improved holding power is awaited. .

JP-A-6-184498

  This invention makes it a subject to provide the (meth) acrylate type polymer which can be used conveniently for the adhesive or adhesive agent with which the retention strength with respect to base materials, such as a metal, was improved.

The present invention
(1) Formula (IV) :

(Wherein R ¹ Is-(R ⁶  ) _m  -(R ⁷  ) _n -(R ⁶  Is the formula (Vb):

And a group represented by R ⁷ Is the formula (Vc):

M and n each independently represents an integer of 5 to 100, and the sum of m and n is 10 to 150. m R ⁶ And n R ⁷ May be combined at random or in blocks. ) Divalent oligomer chain represented by R) ² Is-(CH ₂ ) _q A divalent aliphatic group represented by-(wherein q represents an integer of 1 to 8), R ^Three Is CH ₂ = C (R ^Four ) -Group (R ^Four Represents a hydrogen atom or a methyl group), x represents an integer of 1 to 10)
(Meth) acrylate polymer represented by
(2) A formula in which a terminal hydroxyl group-containing compound represented by formula (I) and (meth) acrylate are reacted at a ratio of 2 to 60 mol of (meth) acrylate per 1 mol of the terminal hydroxyl group-containing compound ( (IV) a process for producing a (meth) acrylate polymer represented by
(3) A pressure-sensitive adhesive containing the (meth) acrylate polymer according to (1), and
(4) Adhesive containing the (meth) acrylate polymer according to (1)
About.

  In the present specification, “acrylic acid and / or methacrylic acid” is referred to as “(meth) acrylic acid”. Further, “acrylate and / or methacrylate” is referred to as “(meth) acrylate”.

  Since the (meth) acrylate polymer of the present invention exhibits excellent holding power against a substrate such as metal, it is a useful compound for pressure-sensitive adhesives and adhesives.

  The terminal hydroxyl group-containing compound of the present invention has the formula (I):

(Wherein R ¹ is a divalent oligomer chain, R ² is a divalent aliphatic group, a divalent aromatic group or a divalent alicyclic group, and x is an integer of 1 to 10)
It is a compound represented by these.

In the formula (I), R ¹ represents a divalent oligomer chain. As a representative example of a divalent oligomer chain, the formula (V):
− (R ⁵ ) _p − (V)
(Wherein R ⁵ is an alkylene group having 2 to 12 carbon atoms, p is an integer of 10 to 150, preferably an integer of 10 to 120, more preferably an integer of 10 to 100)
The oligomer chain | strand represented by these is mentioned. Preferable examples of the divalent oligomer chain include the formula (Va):
− (R ⁶ ) _m − (R ⁷ ) _n − (Va)
Wherein R ⁶ and R ⁷ are each independently an alkylene group having 1 to 6 carbon atoms, m and n are each independently an integer of 5 to 100, and the sum of m and n is 10 to 10 150. m R ⁶ and n R ⁷ may be bonded at random or may be bonded by a block)
The oligomer chain | strand represented by these is mentioned.

R ⁶ and R ⁷ are each independently an alkylene group having 1 to 6 carbon atoms. Among them, an alkylene group having 3 to 6 carbon atoms is preferable, and a butylene group is more preferable. Further, R ⁶ is represented by the formula (Vb):

R ⁷ is a group represented by the formula (Vc):

It is still more preferable that it is group represented by these.

  m and n are each independently an integer of 5 to 100, preferably an integer of 5 to 70. The sum of m and n is preferably 10 to 150, more preferably 10 to 120, and still more preferably 10 to 100.

m R ⁶ and n R ⁷ may be bonded at random or may be bonded at a block, but are preferably bonded at random from the viewpoint of uniform properties. .

R ² represents a divalent aliphatic group, a divalent aromatic group or a divalent alicyclic group.
Examples of the divalent aliphatic group include an aliphatic group having 3 to 12 carbon atoms. Typical examples of the divalent aliphatic group include C3-C12 alkylene groups such as a hexamethylene group, a trimethylhexamethylene group, a tetramethylene group, a pentamethylene group, a heptamethylene group, and an octamethylene group. It is done.

  Examples of the divalent aromatic group include a divalent aromatic group having 6 to 18 carbon atoms. Representative examples of the divalent aromatic group include, for example, an arylene group having 6 to 18 carbon atoms such as a methylphenylene group, a diphenylmethylene group, a xylylene group, a tetramethylxylylene group, a naphthylene group, a phenylene group, and a diphenylene group. Can be mentioned.

  As an example of a bivalent alicyclic group, a C3-C12 alicyclic group is mentioned. Representative examples of the divalent alicyclic group include cycloalkylene groups having 3 to 12 carbon atoms such as a norbornene group, an isophorone group, a cyclohexyl group, a methylcyclohexyl group, an ethylcyclohexyl group, and a propylcyclohexyl group.

Examples of suitable R ² include the formula: — (CH ₂ ) _q — (wherein q is an integer of 1 to 8, preferably an integer of 2 to 6, more preferably an integer of 3 to 6, more preferably 6).
x represents an integer of 1 to 10, preferably an integer of 1 to 6.

  The hydroxyl group-containing compound represented by formula (I) comprises a diol represented by formula (II) and a diisocyanate represented by formula (III) at a ratio of 0.5 to 1 mole of diisocyanate per mole of diol. It can be obtained by reacting.

In the diol represented by the formula (II), R ¹ may be the same as described above. Representative examples of the diol represented by the formula (II) include hydrogenation of a diene diol obtained by polymerizing a conjugated diene having two hydroxyl groups and, if necessary, another copolymerizable monomer, and the diene diol. Diols obtained by this are mentioned.

  Specific examples of the diol represented by the formula (II) include polyisoprene having two hydroxyl groups, polybutadiene having two hydroxyl groups, styrene-butadiene copolymer having two hydroxyl groups, acrylonitrile-butadiene copolymer having two hydroxyl groups, Polychloroprene having two hydroxyl groups, poly (oxypropylene) having two hydroxyl groups, poly (oxytetramethylene) glycol having two hydroxyl groups, polyolefin glycol having two hydroxyl groups, poly-ε-caprolactone having two hydroxyl groups , And hydrogenated products thereof. Among these, polybutadiene having 2 hydroxyl groups which may be hydrogenated and polyisoprene having 2 hydroxyl groups which may be hydrogenated are more preferable.

Examples of preferred diols include the formula (IIa):
_{^{HO- (R 5) p -OH (}} IIa)
(Wherein R ⁵ and p are the same as above)
The diol represented by these is mentioned. Examples of more preferred diols are those of formula (IIb):
HO— (R ⁶ ) _m — (R ⁷ ) _n —OH (IIb)
(Wherein R ⁶ , R ⁷ , m and n are the same as above)
The diol represented by these is mentioned.

In the diisocyanate represented by the formula (III), R ² may be the same as described above. Specific examples of the diisocyanate represented by the formula (III) include tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, Examples include aromatic, aliphatic or alicyclic diisocyanates such as tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the present invention is illustrative It is not limited to only.

  The amount of the diisocyanate represented by the formula (III) per mole of the diol represented by the formula (II) is 0.5 to 1 from the viewpoint of operability in consideration of reaction control and thickening of the resulting reaction mixture. It is desirable that the molar ratio is 0.5 to 0.8 mol.

  The reaction between the diol represented by the formula (II) and the diisocyanate represented by the formula (III) can be carried out, for example, in an organic solvent.

  Examples of the organic solvent include n-hexane and toluene, but the present invention is not limited to such examples.

  The amount of the organic solvent is usually 10 to 100 parts by weight, preferably 20 to 40 parts by weight with respect to 100 parts by weight of the diol represented by the formula (II).

  The reaction temperature between the diol represented by the formula (II) and the diisocyanate represented by the formula (III) is usually preferably the reflux temperature, more specifically 75 to 85 ° C.

  Moreover, it is preferable that the atmosphere in the case of reaction is inert gas atmosphere, such as nitrogen gas and argon gas, for example.

  The end point of the reaction is, for example, when the reaction is performed such that the amount of diisocyanate per mole of the diol represented by the formula (II) is 0.5 mole, the conversion rate of the hydroxyl group of the diol represented by the formula (II) Can be taken as 50% or more.

  Thus, the terminal hydroxyl group-containing compound represented by the formula (I) can be obtained. The obtained terminal hydroxyl group-containing compound represented by the formula (I) is a useful compound as an intermediate for producing the (meth) acrylate polymer represented by the formula (IV).

  The (meth) acrylate polymer represented by the formula (IV) can be obtained by esterifying or transesterifying the terminal hydroxyl group-containing compound represented by the formula (I) with (meth) acrylate. Among these reactions, a transesterification reaction is preferable from the viewpoint of production efficiency.

  Specific examples of (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate n-butyl, ( Examples include (meth) acrylates having 1 to 4 carbon atoms in the alkyl ester moiety such as (meth) acrylate isobutyl and (meth) acrylate t-butyl. Among these, methyl (meth) acrylate is preferable because it is inexpensive and has excellent versatility.

  The amount of (meth) acrylate per 1 mol of the terminal hydroxyl group-containing compound represented by the formula (I) is 2 to 60 mol, preferably 5 to 20 mol, from the viewpoint of reaction rate and production efficiency.

  The reaction between the terminal hydroxyl group-containing compound represented by the formula (I) and (meth) acrylate can be performed, for example, in an organic solvent.

  Examples of the organic solvent include n-hexane and toluene, but the present invention is not limited to such examples.

  The amount of the organic solvent is usually 10 to 100 parts by weight, preferably 20 to 40 parts by weight with respect to 100 parts by weight of the terminal hydroxyl group-containing compound represented by the formula (I).

  The reaction mixture obtained by the reaction of the diol represented by the formula (II) and the diisocyanate represented by the formula (III) contains the produced terminal hydroxyl group-containing compound represented by the formula (I). Therefore, the reaction mixture may be used as it is for the reaction between the terminal hydroxyl group-containing compound represented by the formula (I) and (meth) acrylate.

  The reaction temperature between the terminal hydroxyl group-containing compound represented by the formula (I) and (meth) acrylate is usually preferably a reflux temperature, more specifically 75 to 85 ° C.

  The atmosphere during the reaction is preferably a gas containing air, oxygen gas or oxygen gas, and more preferably air or oxygen gas, from the viewpoint of suppressing polymerization of (meth) acrylate.

  In the reaction of the terminal hydroxyl group-containing compound represented by the formula (I) with (meth) acrylate, a polymerization inhibitor can be used.

  Specific examples of the polymerization inhibitor include 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4 -Benzooxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine N-oxy radical compounds such as -N-oxyl; hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol, 2,2-methylenebis (4-ethyl-6-t-butylphenol), 2.6-di-t-butyl-N, N-methylamino-p-cresol, 2,4-dimethyl-6-t-butylphenol, 4-t-butylcatechol, 4,4'-thio-bis (3-methyl -6-t-Buchi Phenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol) and the like; phenothiazine, N, N′-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, N, Amino compounds such as N′-di-β-naphthyl-p-phenylenediamine and N-phenyl-N′-isopropyl-p-phenylenediamine; 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, Hydroxyamine compounds such as 4-hydroxy-2,2,6,6-tetramethylpiperidine; quinone compounds such as benzoquinone and 2,5-di-t-butylhydroquinone, cuprous chloride, copper dimethyldithiocarbamate, etc. These may be used alone or in combination of two or more.

  Among the polymerization inhibitors, an N-oxy radical compound, a phenol compound, an amino compound, and a hydroxyl group are used from the viewpoint of effectively suppressing not only the (meth) acrylate but also the (meth) acrylate polymer that is the target compound. Amine compounds are preferred, and these may be used alone or in combination of two or more. Among these, from the viewpoint of effectively suppressing polymerization of (meth) acrylate and the target compound (meth) acrylate-based polymer, the N-oxy radical-based compound, or the N-oxy radical-based compound and the phenol-based compound. Is more preferable.

  In addition, the said polymerization inhibitor can also be used together with another polymerization inhibitor. Thus, when the said polymerization inhibitor and another polymerization inhibitor are used together, the more superior polymerization inhibitory effect may be expectable by the synergistic effect by both combined use.

  The amount of the polymerization inhibitor is usually 0.0005 to 0.5 parts by weight, preferably 0 with respect to 100 parts by weight of the total amount of the terminal hydroxyl group-containing compound represented by formula (I) and (meth) acrylate. 0.005 to 0.3 part by weight is desirable.

  The end point of the reaction can be, for example, when the hydroxyl group conversion rate (liquid chromatography analysis) of the terminal hydroxyl compound represented by the formula (I) is 95% or more.

  After completion of the reaction, it is preferable from the viewpoint of operability to add toluene to the obtained reaction mixture and then concentrate.

Further, the reaction mixture includes, for example, hydrotalcite [Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O] (Kyowa Chemical Industry Co., Ltd., KW500PL) together with an organic solvent such as toluene and acetone and water. From the viewpoint of removing the catalyst used in the transesterification, it is preferable that the catalyst is added and heated at a temperature of about 75 to 85 ° C. for 1 to 5 hours and refluxed.

  Thereafter, for example, by dehydrating under reduced pressure, filtering the reaction mixture with a filter, and concentrating the resulting filtrate under reduced pressure, the formula (IV):

(In the formula, R ¹ , R ² and x are the same as above. R ³ is a CH ₂ ═C (R ⁴ ) — group (R ⁴ represents a hydrogen atom or a methyl group).
(Meth) acrylate polymer represented by the following can be recovered.

  The (meth) acrylate polymer represented by the formula (IV) thus obtained is a useful compound for pressure-sensitive adhesives, adhesives and the like.

  The (meth) acrylate polymer represented by the formula (IV) is added with, for example, organic solvents, antioxidants, flame retardants, antistatic agents, fillers, leveling agents, stabilizers, reinforcing agents, matting agents, etc. By doing so, it can be suitably used for a pressure-sensitive adhesive, an adhesive and the like.

  In addition, an epoxy compound, an aziricin compound, a melamine compound, an isocyanate compound, a chelate compound etc. can be added to the said adhesive agent as needed.

  The (meth) acrylate polymer represented by the formula (IV) is suitably used as an adhesive by adding, for example, an organic solvent, rosin, rosin ester, hydrogenated petroleum resin, hydrocarbon resin, fatty acid ester, etc. can do.

  Examples of the organic solvent include alcohols such as ethyl acetate, toluene, xylene, methanol, ethanol, and butanol, ketones such as acetone, methyl isobutyl ketone, and methyl ethyl ketone, and ethers such as butyl cellosolve. It is not limited to illustration only. The amount of the organic solvent is usually preferably about 1 to 50 parts by weight per 100 parts by weight of the (meth) acrylate polymer represented by the formula (IV).

  In addition, when the (meth) acrylate polymer represented by the formula (IV) of the present invention is used for an adhesive or an adhesive, examples of applicable substrates include polyvinyl chloride, polybutadiene, polyurethane, polyester, polyolefin The base material which consists of resin, such as a metal plate, a glass plate, etc. are mentioned, However, This invention is not limited only to this illustration.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited to such examples.

Example 1 (Reference Example)
In a 3000 mL five-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas blowing tube, 1200 g (0.35 mol) of hydrogenated polybutadiene polyol (average molecular weight 3430, hydroxyl value 32.8 mgKOH / g) 420 g of n-hexane was charged, and a mixed solution of 29 g (0.17 mol) of hexamethylene diisocyanate and 29 g of n-hexane was added dropwise over 30 minutes under reflux (77 ° C.).

  The reaction was carried out under reflux, and the reaction was terminated when the hydroxyl group conversion of the hydrogenated polybutadiene diol reached 51.2 mol%.

  The solvent was distilled off from the obtained reaction mixture under reduced pressure to obtain a terminal hydroxyl group-containing compound having a solid content of 99% by weight. Since the produced terminal hydroxyl group-containing compound has the following physical properties, the formula:

(In the formula, m represents an integer of 43, n represents an integer of 24, and x represents 1 or 3)
It was confirmed that it is a compound represented by.

(1) Molecular weight (polymerization average molecular weight in terms of standard polystyrene molecular weight)
Gel permeation chromatography (GPC) [manufactured by Tosoh Corporation, product number: HLC-8220GPC], columns: TSK-GEL, G4000HXL, 7.8φ × 300mm; TSK-GEL, G3000HXL, 7.8φ × 300mm; and TSK-GEL , G2000HXL, 7.8φ × 300 mm × 2 [above, manufactured by Tosoh Corporation, product number]. The results are shown below.
[Molecular weight distribution (GPC%)]
26457 (45%): x = 3
12084 (26%): x = 1
06192 (29%): x = 0 (unreacted hydrogenated polybutadiene polyol)

(2) Infrared absorption spectrum (cm ^-1 )
Product name: Paragon 1000FT-IR ATR method, manufactured by PerkinElmer Japan Co., Ltd. The results are shown below.

IR (cm ^-1 ): 3342, 2959, 2920, 2853, 1703, 1516, 1461, 1379, 1255, 1144, 1056, 937, 771, 721, 632, 622, 606, 597, 586, 576, 564, 559 , 548, 538, 527, 516, 506, 500, 491, 479, 461

As is apparent from the measurement data of the infrared absorption spectrum, since no isocyanate-based absorption was observed in the vicinity of 2300 cm ⁻¹ , the disappearance of isocyanate groups was confirmed, and urethane was observed at 1703 cm ⁻¹ and 1516 cm ⁻¹ . The formation of a urethane bond was confirmed from the fact that absorption based on OH was observed, and the presence of OH group was confirmed from the absorption based on alcohol observed at 3342 cm ⁻¹ .

(3) Nuclear magnetic resonance spectrum ( ¹ H-NMR)
Measurement was performed using JEOL Ltd., product number: ECX-500, measurement solvent: CDCL ₃ . The results are shown in Table 1.

(4) Hydroxyl value Measured by adding acetylating reagent to sample, heating in boiling water bath for 1 hour, allowing to cool, adding 1% phenolphthalein pyridine solution as indicator, and titrating with potassium hydroxide ethanol solution. did. The results are as follows.

-Hydroxyl value of hydrogenated polybutanediene polyol: 32.8 mgKOH / g
-Hydroxyl value of the mixture of terminal hydroxyl group-containing compounds: 16.9 mg KOH / g
・ Hydroxyl conversion determined from hydroxyl value: 48.6%

Example 2
A terminal hydroxyl group-containing compound was prepared in the same manner as in Example 1, and 292.8 g (3.40 mol) of methyl acrylate, 0.36 g of methoquinone and 0.24 g of hydroxytempo were added to the resulting reaction mixture, And dehydrated at reflux. Thereafter, 0.60 g of tetra-n-butoxytitanium was added to this reaction mixture, and the reaction was carried out at 77-80 ° C. while removing the generated methanol and stirring, and the hydroxyl group conversion of the terminal hydroxyl group-containing compound (analysis by liquid chromatography) ) Was 99.3%, and concentrated while dropping 352 g of toluene (distilled liquid amount 107 g)

Next, 918 g of toluene, 64 g of acetone, 13 g of ion-exchanged water, and hydrotalcite [Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O] [manufactured by Kyowa Chemical Industry Co., Ltd., trade name: Kyoward 500PL] was added and heated to reflux at 78-80 ° C. for 2 hours. Subsequently, dehydration was performed while refluxing under reduced pressure, and then the reaction mixture was filtered with a 1 L pressure filter.

  The obtained filtrate was concentrated under reduced pressure at 77 to 83 ° C. to obtain 1137 g of an acrylate polymer (yield: 92%).

  The physical properties of the produced acrylate polymer were examined in the same manner as in Example 1, and the following physical properties were obtained.

(In the formula, m represents an integer of 43, n represents an integer of 24, and x represents 1 or 3)
It was confirmed that an acrylate polymer represented by

(1) Molecular weight (weight average molecular weight in terms of standard polystyrene molecule)
The results of the molecular weight of the produced acrylate polymer are as follows.
Molecular weight distribution (GPC%)
26457 (45%) x = 3
12237 (26%) x = 1
06291 (29%) x = 0

(2) Infrared absorption spectrum The measurement results of the infrared absorption spectrum of the produced acrylate polymer are as follows.
IR (cm ^-1 ): 2959, 2921, 2853, 1731, 1636, 1510, 1461, 1406, 1379, 1294, 1268, 1187, 1144, 1059, 984, 963, 809, 772, 722, 622, 608, 596 , 587, 575, 560, 548, 537, 528, 516, 510, 488, 479, 461, 454

As is apparent from the measurement data of the infrared absorption spectrum, since no isocyanate-based absorption was observed in the vicinity of 2300 cm ⁻¹ , the disappearance of isocyanate groups was confirmed, and urethane was observed at 1636 cm ⁻¹ and 1510 cm ⁻¹ . The presence of a urethane bond was confirmed from the observation of the absorption based on γ and the presence of a vinyl group was confirmed from the observation of the absorption based on the vinyl group at 1731 cm ⁻¹ .

(3) Nuclear magnetic resonance spectrum ( ¹ H-NMR)
Table 2 shows the measurement results of the nuclear magnetic resonance spectrum of the produced acrylate polymer.

(4) Ester value To 2.5 g of the sample (produced acrylate polymer), 20 mL of tetrahydrofuran and 15 mL of 0.5N potassium hydroxide ethanol solution were added, and the resulting mixture was added to a 100 mL flask equipped with a reflux condenser. It was put in and heated for 2 hours so that the contents boiled lightly on a water bath. After cooling to about room temperature, 20 mL of tetrahydrofuran, 20 mL of 0.5N hydrochloric acid solution and phenol red as an indicator were added.

  Next, the ester value was calculated | required by titrating with the 1.0N sodium hydroxide solution to the obtained solution. The results are shown below.

Ester value of acrylate polymer: 15.9 mg KOH / g
Hydroxyl conversion determined from ester value: 94.1%

Example 3
70 parts by weight of the acrylate polymer obtained in Example 2 and 30 parts by weight of isobornyl are mixed, and 5 parts by weight of a curing agent [manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Dycuror 1173] is added to the obtained mixture. And mixed to obtain an ultraviolet curable adhesive.

The obtained ultraviolet curable pressure-sensitive adhesive was applied to an untreated polyethylene terephthalate film (thickness: 50 μm) with an applicator so that the film thickness was 50 μm, and an ultraviolet irradiation device [trade name, manufactured by Eye Graphics Co., Ltd. : UV power supply for ultraviolet light, model: UB031-5BM-60Hz], and under the conditions of 120 W / cm (3 kW high pressure mercury lamp), 10 cmH, 10 m / mm, and PASS (total 600 mJ / cm ² ) Irradiated and cured to obtain an adhesive sheet.

  It was 0 deviation mm / 3days when the retention strength of the obtained adhesive sheet was measured in accordance with the following method.

[Method for measuring holding force]
Adhesive sheet is attached to the polishing plate of tin plate, and is attached so that the area becomes 25 mm × 25 mm, a load of 1 kg is applied at room temperature, and the holding power after 72 hours according to JIS Z 0237 ( Deviation mm) was measured.

  From the above, it can be seen that the acrylate polymer exhibits excellent holding power, and can be suitably used for, for example, pressure-sensitive adhesives and adhesives for various substrates.

  The (meth) acrylate polymer of the present invention is a compound useful for, for example, pressure-sensitive adhesives and adhesives for various substrates.

Claims (4)

Formula (IV):

Wherein R ¹ is-(R ⁶ ) _m- (R ⁷ ) _n- (R ⁶ is the formula (Vb):

R ⁷ is a group represented by the formula (Vc):

M and n each independently represents an integer of 5 to 100, and the sum of m and n is 10 to 150. m R ⁶ and n R ⁷ may be bonded at random or may be bonded in a block. ) R ² represents a divalent aliphatic group represented by — (CH ₂ ) _q — (wherein _q represents an integer of 1 to 8), and R ³ represents CH. ₂ = C (R ⁴ ) — group (R ⁴ represents a hydrogen atom or a methyl group), x represents an integer of 1 to 10)
A (meth) acrylate polymer represented by: Formula (I):

Wherein R ¹ is-(R ⁶ ) _m- (R ⁷ ) _n- (R ⁶ is the formula (Vb):

R ⁷ is a group represented by the formula (Vc):

M and n each independently represents an integer of 5 to 100, and the sum of m and n is 10 to 150. m R ⁶ and n R ⁷ may be bonded at random or may be bonded in a block. ) R ² is a divalent aliphatic group represented by — (CH ₂ ) _q — (wherein q is an integer of 1 to 8) , x is 1 to (Indicates an integer of 10)
Wherein the terminal hydroxyl group-containing compound and (meth) acrylate are reacted at a ratio of 2 to 60 moles of (meth) acrylate per mole of the terminal hydroxyl group-containing compound (IV):

(In the formula, R ¹ , R ² and x are the same as above. R ³ represents a CH ₂ ═C (R ⁴ ) — group (R ⁴ represents a hydrogen atom or a methyl group)).
The manufacturing method of the (meth) acrylate type polymer represented by these. A pressure-sensitive adhesive comprising the (meth) acrylate polymer according to claim 1 . An adhesive comprising the (meth) acrylate polymer according to claim 1 .