Crosslinkable polymer and composition

Abstract

To provide a novel crosslinkable polymer that retains excellent properties of polyparahydroxystyrene such as alkali solubility, heat resistance, and wear resistance, enabling photo-curing as well as heat-curing.SOLUTION: The present invention provides a crosslinkable polymer produced by reacting phenolic hydroxyl groups of polyparahydroxystyrene with an isocyanate compound having one or more photopolymerizable groups.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention aims to provide a novel crosslinkable polymer which can be cured by heat or light by reacting poly(parahydroxystyrene) with an isocyanate monomer. [Background technology]

[0002] Polyparahydroxystyrene is widely used as a photosensitive material because of its excellent alkali solubility, good resolution, and excellent etching resistance. It also has excellent rust prevention effects when used as a surface treatment agent for steel, aluminum, copper, etc. Taking advantage of these properties, it is used in many products such as printed wiring boards, adhesives, PS printing plates, metal surface treatment agents, photoresists, and sealants.

[0003] For example, a polymer obtained by modifying the hydroxyl groups of poly-para-hydroxystyrene is used as a polymer component of a chemically amplified positive resist composition. This is achieved by introducing an acid-labile group into the hydroxyl groups of poly-para-hydroxystyrene, and although the hydroxystyrene derivative itself is insoluble or poorly soluble in an alkaline aqueous solution, the acid-labile group is cleaved by the action of an acid, making it soluble in an alkaline aqueous solution. This is utilized to form a pattern (see Patent Document 1). Also, in order to obtain a resin material with excellent heat resistance and abrasion resistance, an addition condensation reaction product between a polymer having a repeating unit derived from parahydroxystyrene and an aldehyde has been reported. According to this, the polymer can be used as a curing agent and can be used in a resin composition for a negative resist (see Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2009-003242 A [Patent Document 2] JP 2018-016713 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, although the polyhydroxystyrene polymers described in Patent Documents 1 and 2 can be used as thermosetting resins, they cannot be used as photosetting resins because the polyparahydroxystyrene polymer itself does not have a photopolymerizable group (carbon-carbon double bond), and therefore have not been applied to resin compositions composed of alkali-soluble resins.

[0006] In view of the above problems, the present invention has synthesized a photocurable polymer derived from poly-para-hydroxystyrene by reacting an isocyanate monomer having one or more photopolymerizable groups with the hydroxyl group of poly-para-hydroxystyrene. This provides a novel crosslinkable polymer that has the excellent properties of poly-para-hydroxystyrene, such as alkali solubility, heat resistance, and abrasion resistance, and can be photocured in addition to being thermocured. Furthermore, the crosslinkable polymer can also serve as a component of a curing agent or crosslinking agent for a composition that requires thermocuring or photocuring. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention mainly has the following configuration. [1] A crosslinkable polymer obtained by reacting polyparahydroxystyrene with an isocyanate compound having one or more photopolymerizable groups, the crosslinkable polymer having structural units represented by the following general formulas (1) and (2):

[0008] [ka]

[0009] (In formula (1), R 1 represents a monovalent group having a (meth)acryloyl group. [2] R in the general formula (1) 1 The crosslinkable polymer according to [1], wherein is a monovalent group having two or more (meth)acryloyl groups. [3] The crosslinkable polymer according to [1] or [2], wherein the polyparahydroxystyrene has a number average molecular weight of 8,000 or less and a weight average molecular weight of 15,000 or less. [4] The crosslinkable polymer according to [1] or [2], wherein the molar ratio of the general formula (1) to the general formula (2) (general formula (1) / general formula (2)) is 0.01 to 50. [5] A composition containing a solvent with a boiling point of 120°C or higher and the crosslinkable polymer described in [1] or [2]. [6] The composition according to [5], having a solids concentration of 20 to 70%. [7] The composition according to [5], which is heat-curable or photo-curable. Effect of the Invention

[0010] According to the crosslinkable polymer of the present invention, by introducing one or more photopolymerizing groups into the phenolic hydroxyl group of polyparahydroxystyrene, a novel polymer that can be heat-cured as well as photocured can be obtained. In particular, by reacting an isocyanate monomer having two or more photopolymerizable groups, a polymer excellent in heat curing, photo curing, and crosslinking properties can be provided. In addition, by adjusting the amount of isocyanate monomer to be reacted, it is possible to easily adjust the excellent alkali solubility of polyparahydroxystyrene and the heat curing, photo curing, and crosslinking properties of the crosslinkable polymer. Therefore, the crosslinkable polymer maintains the alkali solubility, heat resistance, and abrasion resistance of polyparahydroxystyrene, and is a novel crosslinkable polymer that is rich in photocuring and crosslinking properties, and can be widely used as a heat curing and photo curing agent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The crosslinkable polymer of the present invention is a crosslinkable polymer (A) having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) (hereinafter sometimes abbreviated as "polymer (A)").

[0012] [ka]

[0013] The copolymer may be a block copolymer or a random copolymer having these structural units, and may further have other structural units. In the above general formula (1), R 1 represents a monovalent group having a (meth)acryloyl group. Here, the (meth)acryloyl group is a general term for an acryloyl group and a methacryloyl group. It is preferable that the polymer (A) has two or more (meth)acryloyl groups, which can improve the thermosetting property, photocuring property, and crosslinking property. Furthermore, R of the polymer (A) 1 More preferably, it has two or more acryloyl groups.

[0014] The polymer (A) can be synthesized, for example, by adding an isocyanate compound having a (meth)acryloyl group to some of the phenolic hydroxyl groups of polyparahydroxystyrene.

[0015] Examples of polyparahydroxystyrene include "Marukalinker (registered trademark)" M manufactured by Maruzen Petrochemical Co., Ltd. and VP Polymer manufactured by Nippon Soda Co., Ltd. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyparahydroxystyrene used are not particularly limited, but it is more preferable that the number average molecular weight (Mn) is 8,000 or less and the weight average molecular weight (Mw) is 15,000 or less.

[0016] Examples of the isocyanate compound include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, etc. Specific examples include "Karenz (registered trademark)" MOI, "Karenz" AOI, "Karenz" MOI-EG, "Karenz" BEI, "Karenz" MOI-BP, "Karenz" MOI-BM, etc., manufactured by Resonac Co., Ltd.

[0017] The catalyst for promoting the addition reaction of the phenolic hydroxyl group and the isocyanate compound is not particularly limited as long as it is a compound containing a metal component and exhibiting urethanization activity, but is preferably an organometallic compound containing one or more metals selected from Fe, Sn, Zr, Ti, and Al. Among them, Sn catalysts, which are easily available and have little temperature dependency in catalytic activity, and one or more metal chelates such as Ti chelate catalysts and Zr chelate catalysts, which are easy to adjust in reactivity, can be used.

[0018] Specifically, the Sn catalyst is not particularly limited, but examples thereof include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diversatate, and dibutyltin bis(acetylacetate).

[0019] The Fe chelate catalyst is not particularly limited, but examples thereof include iron trisacetylacetonate, etc.; Zr chelate catalysts include zirconium tetraacetylacetonate, zirconium ethylacetoacetate, etc.; Ti chelate catalysts include titanium acetylacetonate, titanium ethylacetoacetate, etc.; and Al chelate catalysts include aluminum trisacetylacetonate, etc.

[0020] In the polymer (A), the molar ratio of the structural unit represented by general formula (2) to the structural unit represented by general formula (1) (general formula (1) / general formula (2)) is preferably in the range of 0.01 to 50. If this ratio is small, the proportion of photopolymerizable groups is small, so that the photocurability and crosslinking functions are reduced, and it is possible to provide a polymer (A) with excellent alkali solubility. On the other hand, if this ratio is large, the proportion of photopolymerizable groups is large, so that the photocurability and crosslinking functions are improved, and it is possible to provide a polymer (A) with excellent crosslinkability.

[0021] The composition of the present invention preferably further contains a solvent. The solvent is not particularly limited, but it is more preferable to use a solvent having a boiling point of 120° C. or more in terms of the reaction temperature during synthesis of the polymer (A) and further workability (volatility) in a solution state. Examples of solvents having a boiling point of 120° C. or more include N,N-dimethylacetamide (boiling point 165° C.), N,N-dimethylformamide (boiling point 153° C.), N-methyl-2-pyrrolidone (202° C.), dimethylimidazolidinone (boiling point 222° C.), dimethylsulfoxide (boiling point 189° C.), γ-butyrolactone (boiling point 204° C.), ethyl lactate (boiling point), 1-ethoxy-2-propanol (boiling point 132° C.), ethylene glycol mono-n-propyl ether (boiling point 151° C.), diacetone alcohol (boiling point 163° C.), and the like. 8°C), tetrahydrofurfuryl alcohol (boiling point 178°C), propylene glycol monomethyl ether acetate (boiling point 146°C), diethylene glycol monoethyl ether acetate (boiling point 156°C), diethylene glycol monomethyl ether (boiling point 194°C), diethylene glycol monoethyl ether acetate (boiling point 218°C), diethylene glycol monobutyl ether (boiling point 230°C), diethylene glycol monobutyl ether acetate (boiling point 247°C), etc.

[0022] Next, the synthesis and production method of the present polymer (A) will be described. The crosslinkable polymer of the present invention is not particularly limited as long as it can uniformly disperse and react the raw materials, and various stirring methods known in the art can be used. For example, a method of stirring using a stirrer can be mentioned. Examples of the stirrer include a general-purpose stirrer, a planetary mixer, a disperser, a dissolver, a mixer, a lab plastomill, and a planetary mixer. The shape of the stirring blade is not particularly limited, but is preferably any of a turbine blade, a paddle blade, a Pfaudle blade, an anchor blade, and a full zone blade.

[0023] The reaction temperature is not particularly limited, but is preferably in the range of 20 to 110°C, and more preferably 60 to 90°C, because the reaction proceeds efficiently and is easy to control. In addition, the temperature may be raised slowly because it is easy to remove heat and control the reaction, or the temperature may be raised to a predetermined temperature after a certain period of reaction at a relatively low temperature of 20 to 60°C. A catalyst may be added during the reaction. In order to prevent the double bonds derived from the isocyanate monomer from reacting, it is preferable to carry out the reaction in an air atmosphere.

[0024] The reaction time is not particularly limited since it varies depending on the amount of catalyst and reaction conditions, but it is preferably performed for 4 to 12 hours, and more preferably for 6 to 12 hours in order to carry out the reaction sufficiently. The end point of the reaction is preferably determined by monitoring the decay of the NCO group using FT-IR or a titration method, and the reaction is continued until the decay stops.

[0025] The method of addition is not particularly limited, but in order to suppress local reactions and gelation regardless of the reaction conditions, it is preferable to add the isocyanate monomer to the polyparahydroxystyrene solution and mix it, and the isocyanate monomer may be added all at once or in portions. In addition, when a catalyst is used, it is preferable to add it after the isocyanate monomer in order to uniformly disperse the isocyanate monomer before the reaction, but the catalyst may be added before the isocyanate monomer in order to uniformly disperse the catalyst. EXAMPLES

[0026] The present invention will be described below with reference to examples and comparative examples. The present invention is not limited to these examples. In addition, "parts" and "%" are based on mass unless otherwise specified.

[0027] (1) Raw materials used <Polyparahydroxystyrene> "Marukalinker (registered trademark)" M manufactured by Maruzen Petrochemical Co., Ltd. was used. ·S-2P Number average molecular weight (Mn) 2,900, Weight average molecular weight (Mw) 5,400 <Isocyanate monomer> "Karens (registered trademark)" manufactured by Resonac Corporation was used. · As an isocyanate monomer having one (meth)acryloyl group, MOI (2-isocyanatoethyl methacrylate) -BEI (1,1-(bisacryloyloxymethyl)ethyl isocyanate) as an isocyanate monomer having two (meth)acryloyl groups.

[0028] (2) Production of polymer (A) (Example 1: Polymer (A-1)) In a reaction vessel equipped with a stirrer, a cooling tube, a thermometer and a gas inlet tube, 30 g of diethylene glycol monobutyl ether acetate (hereinafter sometimes abbreviated as "BCA") was placed, and 20 g (7 mmol) of parahydroxystyrene polymer (manufactured by Maruzen Petrochemical Co., Ltd., trade name "Marukalinker (registered trademark)" M S-2P") was added while stirring, and the mixture was heated to 60°C and stirred at 60°C for 3 hours to completely dissolve. Then, 2 g (10 mmol) of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (manufactured by Resonac Co., Ltd., trade name "Kalends (registered trademark)" BEI") was added, and 0.02 g of dibutyltin dilaurate (IV) was added as a catalyst, and the mixture was stirred at 80°C for 8 hours under an air atmosphere to carry out a polymerization reaction, thereby obtaining a solution of polymer (A-1). The polymer (A-1) has a structural unit represented by general formula (1) and a structural unit represented by general formula (2) in a ratio of general formula (1) / general formula (2)=0.06, and R 1 is a polymer (A) having two acryloyl groups.

[0029] (Example 2: Polymer (A-2)) 20 g of "BCA" was placed in a reaction vessel equipped with a stirrer, a cooling tube, a thermometer, and a gas inlet tube, and 20 g (7 mmol) of parahydroxystyrene polymer (manufactured by Maruzen Petrochemical Co., Ltd., trade name "Marukalinker (registered trademark)" M S-2P) was added while stirring, and the mixture was heated to 60°C and stirred at 60°C for 3 hours to completely dissolve. Then, 12 g (50 mmol) of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (manufactured by Resonac Co., Ltd., trade name "Kalends (registered trademark)" BEI") was added, and 0.02 g of dibutyltin (IV) dilaurate was added as a catalyst, and the mixture was stirred at 80°C for 8 hours in an air atmosphere to carry out a polymerization reaction, thereby obtaining a solution of polymer (A-2). The polymer (A-2) has a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) in a ratio of the general formula (1) / the general formula (2)=0.4, and R 1 is a polymer (A) having two acryloyl groups.

[0030] (Example 3: Polymer (A-3)) A solution of polymer (A-3) was obtained in the same manner as in Example 2, except that 8 g (50 mmol) of 2-isocyanatoethyl methacrylate (manufactured by Resonac Corporation, product name "Karenz MOI") was used instead of 12 g (50 mmol) of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (manufactured by Resonac Corporation, product name "Karenz BEI"). Polymer (A-3) has a structural unit represented by general formula (1) and a structural unit represented by general formula (2) in a ratio of general formula (1) / general formula (2) = 0.4, and R in general formula (1) 1 is a polymer (A) having one methacryloyl group.

[0031] (Example 4: Polymer (A-4)) 20 g of "BCA" was placed in a reaction vessel equipped with a stirrer, a cooling tube, a thermometer, and a gas inlet tube, and 20 g (7 mmol) of parahydroxystyrene polymer (manufactured by Maruzen Petrochemical Co., Ltd., trade name "Marukalinker (registered trademark)" M S-2P) was added while stirring, and the mixture was heated to 60°C and stirred at 60°C for 3 hours to completely dissolve. Then, 28 g (117 mmol) of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (manufactured by Resonac Co., Ltd., trade name "Kalends (registered trademark)" BEI") was added, and 0.02 g of dibutyltin (IV) dilaurate was added as a catalyst, and the mixture was stirred at 80°C for 8 hours in an air atmosphere to carry out a polymerization reaction, thereby obtaining a solution of polymer (A-4). Polymer (A-4) has a structural unit represented by general formula (1) and a structural unit represented by general formula (2) in a ratio of general formula (1) / general formula (2)=2.3, and R 1 is a polymer (A) having two acryloyl groups.

[0032] (Example 5: Polymer (A-5)) 20 g of "BCA" was placed in a reaction vessel equipped with a stirrer, a cooling tube, a thermometer, and a gas inlet tube, and 20 g (7 mmol) of parahydroxystyrene polymer (manufactured by Maruzen Petrochemical Co., Ltd., trade name "Marukalinker (registered trademark)" M S-2P) was added while stirring, and the mixture was heated to 60°C and stirred at 60°C for 3 hours to completely dissolve. Then, 38 g (158 mmol) of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (manufactured by Resonac Co., Ltd., trade name "Kalends (registered trademark)" BEI") was added, and 0.02 g of dibutyltin (IV) dilaurate was added as a catalyst, and the mixture was stirred at 80°C for 8 hours in an air atmosphere to carry out a polymerization reaction, thereby obtaining a solution of polymer (A-5). Polymer (A-5) has a structural unit represented by general formula (1) and a structural unit represented by general formula (2) in a ratio of general formula (1) / general formula (2)=19, and R 1 is a polymer (A) having two acryloyl groups.

[0033] (Example 6: Polymer (A-6)) 20 g of "BCA" was placed in a reaction vessel equipped with a stirrer, a cooling tube, a thermometer, and a gas inlet tube, and 20 g (7 mmol) of parahydroxystyrene polymer (manufactured by Maruzen Petrochemical Co., Ltd., trade name "Marukalinker (registered trademark)" M S-2P) was added while stirring, and the mixture was heated to 60°C and stirred at 60°C for 3 hours to completely dissolve. Then, 39 g (163 mmol) of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (manufactured by Resonac Co., Ltd., trade name "Kalends (registered trademark)" BEI") was added, and 0.02 g of dibutyltin (IV) dilaurate was added as a catalyst, and the mixture was stirred at 80°C for 8 hours in an air atmosphere to carry out a polymerization reaction, thereby obtaining a solution of polymer (A-6). Polymer (A-6) has a structural unit represented by general formula (1) and a structural unit represented by general formula (2) in a ratio of general formula (1) / general formula (2)=49, and R 1 is a polymer (A) having two acryloyl groups.

[0034] Comparative Example 1 Polyparahydroxystyrene polymer S-2P was used.

[0035] (1) Analysis and evaluation of polymer (A) The physical properties of the obtained polymer (A) solution were analyzed as follows, and the results are shown in Table 1. (a) Evaporation residue The obtained polymer (A) solution was dried by heating at 200° C. for 1 hour, and the solid content of polymer (A) was calculated from the change in weight before and after drying.

[0036] (b) Weight average molecular weight The polymer (A) obtained was subjected to gel permeation chromatography (GPC) measurement using a differential refractometer according to the following procedure.

[0037] 30 mg of polymer (A) and 10 ml of tetrahydrofuran (THF) were placed in a sample bottle and completely dissolved. The solution was filtered through a PTFE cartridge filter (0.5 μm) to prepare a sample for GPC measurement. The GPC measurements were performed using THF as the developing solvent at a column temperature of 40°C. A third-order approximation curve using standard polystyrene with known molecular weights was used as the calibration curve, and analysis was performed. The measurement device used was Shimadzu Corporation's LC-20AD, and the analysis was performed using Shimadzu Corporation's "LabSolutions."

[0038] (c) Viscosity The viscosity of the obtained polymer (A) solution at 25°C was measured by the cone-plate viscometer method in accordance with the description of JIS K 5600-2-3 at a temperature of 25°C, a 3° plate, and a rotation speed of 20 rpm. The measuring device used was the RE-215U manufactured by Toki Sangyo Co., Ltd.

[0039] (d) Isocyanate conversion reaction rate The reaction conversion rate refers to the rate at which the isocyanate monomer is converted.

[0040] The amount of isocyanate in the polymer (A) solution was measured in accordance with the n-dibutylamine method described in JIS K 1556. The reaction conversion rate was calculated by dividing the actually measured amount of isocyanate by the theoretical amount of isocyanate.

[0041] Evaluation of curability of the obtained polymer (A) The curability of the photopolymerizable group introduced into the obtained polymer (A) was confirmed by the following procedure, and the results are shown in Table 2.

[0042] To the obtained polymer (A) solution, 0.5 parts of a photopolymerization initiator (Irgacure 184, manufactured by Chiba Specialty Chemicals) was added per 100 parts of polymer (A). The mixture was mixed using a rotary-revolution vacuum mixer "Awatori Rentaro" (registered trademark) ARE-310 (manufactured by Thinky Corporation). The obtained solution was applied to one side of a non-adhesive polyethylene terephthalate film (manufactured by Toray Industries, Inc., U40, 125 μm thick) so that the thickness after curing was 3 μm, and after removing the solvent, the film was irradiated with ultraviolet light using a high-pressure mercury lamp irradiation device (HC-66, manufactured by Sen Specialty Light Source Co., Ltd.) and cured. The irradiation exposure was performed at 2400 mJ / cm. The obtained film was used to evaluate the alkali resistance according to the following procedure.

[0043] A 1% or 5% potassium hydroxide solution was prepared, and 2 to 3 drops were dropped onto the obtained film using a dropper. The film was left to stand for 1 minute, after which the droplets were wiped off and the state of the film was confirmed. Based on the results, the curability was evaluated according to the following criteria. ◯: No change in film condition (hardened) △: The film has lost its luster and is partially dissolved (insufficient curing). ×: The film was dissolved (not cured).

[0044] As a result of the curing evaluation, it was confirmed that polyparahydroxystyrene is not photocurable, whereas crosslinked polymer (A) obtained by reacting polyparahydroxystyrene with isocyanate monomer has very high curing properties. Crosslinked polymer (A) is a new polymer that can be thermoset or photocured. By adding it as a crosslinking agent itself or using it as a polymer component of a composition in a process that requires thermosetting or photocuring, it is expected to provide excellent heat resistance and abrasion resistance. In addition, in a process that requires alkaline development, it is expected to be a material that can achieve both strong alkaline development and advanced patterning by adjusting the amount of isocyanate monomer in polyparahydroxystyrene. The evaluation results are shown in Tables 1 and 2.

[0045] [Table 1]

[0046] [Table 2] [Industrial Applicability]

[0047] The crosslinkable polymer according to the present invention has excellent curability and can be used as a curing agent. It can also be suitably used as a polymer component of a thermosetting or photocurable composition. For example, it can be suitably used as a resin for positive-type or negative-type resist.

Claims

1. A crosslinkable polymer obtained by reacting polyparahydroxystyrene with an isocyanate compound having one or more photopolymerizable groups, the crosslinkable polymer having structural units represented by the following general formulas (1) and (2): 【Chemistry 1】 (In formula (1), R １ represents a monovalent group having a (meth)acryloyl group.

2. R in the general formula (1) １ 2. The crosslinkable polymer according to claim 1, wherein is a monovalent group having two or more (meth)acryloyl groups.

3. 3. The crosslinkable polymer according to claim 1, wherein the polyparahydroxystyrene has a number average molecular weight of 8,000 or less and a weight average molecular weight of 15,000 or less.

4. The crosslinkable polymer according to claim 1 or 2, wherein the molar ratio of the general formula (1) to the general formula (2) (general formula (1) / general formula (2)) is 0.01 to 50.

5. A composition comprising a solvent having a boiling point of 120° C. or higher and the crosslinkable polymer according to claim 1 or 2.

6. The composition according to claim 5, having a solids concentration of 20 to 70%.

7. The composition of claim 5 which is heat curable or photocurable.

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