TW202344592A - Liquid polymerizable composition and curable resin composition using the same - Google Patents

Abstract

An object of the present invention is to provide a liquid polymerizable composition capable of imparting an appropriate viscosity to a 2-methylene-1,3-dicarbonyl compound without impairing curability. The polymerizable composition of the present invention contains (a) a 2-methylene-1,3-dicarbonyl compound and (b) a specific (meth)acrylate polymer.

Description

Liquid polymerizable composition and curable resin composition using the same

The present invention relates to a liquid polymerizable composition and a curable resin composition using the liquid polymerizable composition.

Nowadays, in the assembly or installation of electronic components used in semiconductor devices, adhesives, sealing materials, etc. containing curable resin compositions are often used for the purpose of maintaining reliability. Semiconductor devices (such as electronic devices such as smartphones) are composed of various electronic modules. The parts constituting these electronic modules are often used, which will degrade their mechanical and electronic properties, positional accuracy, etc. due to heat. Material. Therefore, the assembly of the above-mentioned electronic modules and the assembly or sealing of electronic devices are preferably performed under lower temperature conditions. Therefore, the adhesives or sealing materials used in the manufacture of the above-mentioned electronic devices or electronic modules are required to exhibit sufficient hardening properties even under low temperature conditions. At the same time, in terms of production costs, it is also required to be hardened in a short time.

In recent years, in order to manufacture such electronic parts, the use of "curable resin compositions containing 2-methylene-1,3-dicarbonyl compounds such as methylene malonate" as adhesives, etc. . Such a curable resin composition can be cured in a short time even at low temperatures ranging from room temperature to 80°C or lower, so adverse effects caused by heat used for curing can be avoided and manufacturing efficiency can be improved.

[Prior technical literature]

[Patent Document]

Patent Document 1: International Publication No. 2020/100530.

Patent Document 2: International Publication No. 2021/049588.

Patent Document 3: International Publication No. 2021/049589.

Patent Document 4: International Publication No. 2021/049590.

The viscosity of the curable resin composition used in manufacturing the above-mentioned electronic parts sometimes requires appropriate adjustment. For example, if there is a concern that the flow of the curable resin composition may cause a decrease in operability or subsequent reliability, or may cause contamination around the application site, a curable resin composition exhibiting a certain degree of high viscosity must be used.

Curable resin compositions containing methylene malonate generally exhibit low viscosity. Therefore, in the above case, it is necessary to have a means to increase the viscosity of the curable resin composition containing methylene malonate.

Several means for adjusting the viscosity of a liquid resin composition are known. For example, Patent Documents 2 to 4 describe adding fumed silica or (meth)acrylate polymer.

However, the inventors of the present invention conducted research and found that adding fumed silica to a curable resin composition containing methylene malonate would significantly extend the gel time of the composition. . Furthermore, the present inventors discovered that a (meth)acrylate polymer cannot be dissolved in a liquid resin composition containing methylenemalonate and may not be used to impart viscosity.

In order to solve the above-mentioned problems of the prior art, an object of the present invention is to provide a liquid polymerizable composition that can impart appropriate viscosity.

Under such circumstances, the present inventors sought to develop a methylenemalonate-containing liquid that can impart an appropriate viscosity to a 2-methylene-1,3-dicarbonyl compound without impairing the hardenability. The hardening resin composition has been studied in depth. As a result, it was surprisingly found that by adding a specific (meth)acrylate polymer to the liquid curable composition, an appropriate viscosity can be imparted to the 2-methylene-1,3-dicarbonyl compound. Based on the above novel findings, the present invention is completed.

The present inventors conducted in-depth research in order to solve the above-mentioned problems, and as a result completed the present invention.

That is, the present invention includes the following inventions, but is not limited thereto.

1. A liquid polymeric composition comprising:

(a) 2-methylene-1,3-dicarbonyl compound having at least one structural unit represented by the following formula (I)

(b) A (meth)acrylate polymer containing one or more repeating units represented by the formula -(CH ₂ -CR ^a R ^b )-, in which R ^a represents a hydrogen atom or a methyl group, and R ^b represents the formula The alkoxycarbonyl group represented by -C(O)OR ^c , R ^c represents an alkyl group with 1 to 6 carbon atoms; however, when it contains only one of the aforementioned repeating units, R ^a and R ^c are not methyl groups at the same time.

2. The liquid polymerizable composition according to the preceding item 1, which contains 0.1 to 20 parts by weight of polymerized (meth)acrylate based on 100 parts by weight of the 2-methylene-1,3-dicarbonyl compound. things.

3. The liquid polymerizable composition according to the preceding paragraph 1 or 2, wherein the (meth)acrylate polymer is selected from the group consisting of copolymers of ethyl methacrylate and methyl methacrylate, ethyl methacrylate One or more of the group consisting of homopolymer of ethyl acrylate and homopolymer of isobutyl methacrylate.

4. The liquid polymerizable composition according to any one of the preceding items 1 to 3, wherein at least part of the (meth)acrylate polymer is dissolved in a 2-methylene-1,3-dicarbonyl compound .

5. The liquid polymerizable composition as described in any one of the preceding items 1 to 4, which further contains a thixotropic agent.

6. A one-liquid curable resin composition containing: the liquid polymerizable composition according to any one of the preceding items 1 to 5; and a polymerization initiator containing a latent alkaline substance.

7. A kit for providing a two-liquid mixed hardening resin composition. The kit includes:

(A) The main agent containing the liquid polymerizable composition described in any one of the preceding paragraphs 1 to 5; and

(B) Hardener containing alkaline substances.

8. The liquid polymerizable composition as described in any one of the preceding paragraphs 1 to 5, the liquid curable resin composition as described in the preceding paragraph 6, or the set as described in the preceding paragraph 7, is used for manufacturing Electronic parts.

9. A cured product obtained by curing the liquid polymerizable composition described in any one of the preceding paragraphs 1 to 5, a liquid curable resin composition described in the preceding paragraph 6, or the set described in the preceding paragraph 7. winner.

10. A semiconductor device containing the hardened material described in the preceding paragraph 9.

11. A method for producing a liquid polymerizable composition, which is used to produce the liquid polymerizable composition described in any one of the preceding paragraphs 1 to 5. The method includes the following steps:

Dissolve (meth)acrylate polymer in a volatile organic solvent to obtain a (meth)acrylate polymer solution; and

The (meth)acrylate polymer solution and the 2-methylene-1,3-dicarbonyl compound were mixed.

The liquid polymerizable composition of the present invention contains a 2-methylene-1,3-dicarbonyl compound and a specific (meth)acrylate polymer. The liquid polymerizable composition of the present invention can impart appropriate viscosity to the 2-methylene-1,3-dicarbonyl compound without impairing curability, so that the curable resin composition can be easily produced.

The embodiments of the present invention will be described in detail below.

The present invention relates to a liquid polymerizable composition. The composition contains:

(a) 2-methylene-1,3-dicarbonyl compound having at least one structural unit represented by the following formula (I)

(b) A (meth)acrylate polymer containing one or more repeating units represented by the formula -(CH ₂ -CR ^a R ^b )-, in which R ^a represents a hydrogen atom or a methyl group, and R ^b represents the formula The alkoxycarbonyl group represented by -C(O)OR ^c , R ^c represents an alkyl group with 1 to 6 carbon atoms; however, when it contains only one of the aforementioned repeating units, R ^a and R ^c are not methyl groups at the same time.

The components contained in the liquid polymerizable composition of the present invention will be described below.

In this specification, "acrylic acid" (or its derivatives) and "methacrylic acid" (or its derivatives) are collectively referred to as "(meth)acrylic acid" and "(meth)acrylate". ”, “(meth)acrylic”, “(meth)acrylyl” and other names. These terms may be used as an independent term, or may be used as part of other terms. For example, the term "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid".

(a) 2-methylene-1,3-dicarbonyl compound

The liquid polymerizable composition of the present invention contains (a) 2-methylene-1,3-dicarbonyl compound. In the present invention, the (a) 2-methylene-1,3-dicarbonyl compound is a compound having at least one structural unit represented by the following formula (I).

(a) The 2-methylene-1,3-dicarbonyl compound contains one or more structural units of the aforementioned formula (I). In one aspect, (a) the 2-methylene-1,3-dicarbonyl compound contains 2 to 6 structural units of the aforementioned formula (I), preferably 2 to 3.

The structural unit of the aforementioned formula (I) includes a vinyl group. In the vinyl group, the π-bonded carbon on one side is covalently bonded with two carbonyl groups, and the π-bonded carbon on the other side is not covalently bonded with the substituent. bond. In such a structure, due to the influence of the carbonyl group, the π-bonded carbon in the vinyl group that is not bonded to a carbonyl group is easily attacked by nucleophiles (that is, the vinyl group will be activated). Therefore, the (a) 2-methylene-1,3-dicarbonyl compound has high polymerizability.

(a) The 2-methylene-1,3-dicarbonyl compound contains the structural unit of the aforementioned formula (I). Therefore, in the presence of a polymerization initiator (typically an alkaline substance), the above-mentioned Aggregation of structural units with each other. When the above-mentioned (a) 2-methylene-1,3-dicarbonyl compound contains "one having two or more structural units of the above-mentioned formula (I) (polyfunctional component)", cross-linking occurs during hardening, and it can Improvements in physical properties such as mechanical properties of hardened materials at high temperatures are expected.

(a) The 2-methylene-1,3-dicarbonyl compound can be used alone or in combination of two or more types. (a) The molecular weight of the 2-methylene-1,3-dicarbonyl compound is preferably 180 to 10,000, more preferably 180 to 5,000, still more preferably 180 to 2,000, still more preferably 220 to 2,000, and still more preferably 220 to 2,000. The best is 220 to 1500, the further better is 240 to 1500, the extra best is 250 to 1500, and the best is 250 to 1000. For example, the method can be based on reverse-phase high-speed liquid chromatography (reverse-phase HPLC), using an ODS column as the column, a mass spectrometer (MS) and a PDA (detection wavelength of 190 to 800 nm) or ELSD as the detector. Calibration, whereby the molecular weight of (a) 2-methylene-1,3-dicarbonyl compound is confirmed, and the molecular weight of (a) 2-methylene-1,3-dicarbonyl compound in the composition as a whole (or in the composition) is confirmed. (total carbonyl compounds) as the weight content of each 2-methylene-1,3-dicarbonyl compound at 1 hour. When the molecular weight of the (a) 2-methylene-1,3-dicarbonyl compound is less than 180, the vapor pressure at 25°C will be too high, and various problems caused by volatile matter may occur. In particular, if volatile substances adhere to peripheral components, they will be hardened by alkali on the surface, thereby contaminating the peripheral components.

(a) The 2-methylene-1,3-dicarbonyl compound may contain polyfunctional components. The term "polyfunctional" means that the (a) 2-methylene-1,3-dicarbonyl compound contains two or more structural units of the aforementioned formula (I). The number of structural units of the aforementioned formula (I) contained in (a) 2-methylene-1,3-dicarbonyl compound is referred to as the (a) 2-methylene-1,3-dicarbonyl compound. The "functional base". (a) Among 2-methylene-1,3-dicarbonyl compounds, those with 1 functional group are called "monofunctional", those with 2 functional groups are called "bifunctional", and those with 3 functional groups are called "monofunctional". It is called "3 senses". Obtained from using (a) 2-methylene-1,3-dicarbonyl compound containing polyfunctional components The physical properties of the hardened product (such as heat resistance or mechanical properties at high temperatures) can be improved through the cross-linked structure. When a polyfunctional component is used, the weight ratio of the polyfunctional component is preferably 0.01 or more when the entire liquid polymerizable composition of the present invention is taken as 1. In one aspect, when the entire liquid polymerizable composition of the present invention is taken as 1, (a) 2-methylene-1,3-dicarbonyl group containing two or more structural units represented by the aforementioned formula (I) The weight ratio of the compounds is preferably 0.01 to 1.00, more preferably 0.05 to 0.99, still more preferably 0.05 to 0.95, particularly preferably 0.10 to 0.90, most preferably 0.10 to 0.80.

(a) When the 2-methylene-1,3-dicarbonyl compound contains polyfunctional components, the hardened product can form a network cross-linked structure. Therefore, it can also be used at high temperatures (especially at temperatures above the glass transition temperature). It will not flow but will maintain a fixed storage elastic modulus. For example, dynamic viscoelasticity (DMA) can be used to evaluate the storage elastic modulus of hardened materials at high temperatures. Generally speaking, when evaluating a hardened product with a cross-linked structure using DMA, a small temperature change in the storage elastic modulus called a plateau is observed over a wide range in a temperature range above the glass transition temperature. area. The storage elastic modulus of the plateau region is evaluated as a quantity related to the cross-linking density (that is, the content rate of the polyfunctional component in the (a) 2-methylene-1,3-dicarbonyl compound).

In one aspect, when the entire liquid polymerizable composition of the present invention is taken as 1, the weight ratio of (a) 2-methylene-1,3-dicarbonyl compound is preferably 0.05 to 0.99, more preferably The range is from 0.10 to 0.94, preferably from 0.20 to 0.84, and particularly preferably from 0.25 to 0.74.

In one aspect, (a) the 2-methylene-1,3-dicarbonyl compound is represented by the following formula (II),

In the formula, X ¹ and X ² each independently represent a single bond, O or NR ³ (in the formula, R ³ represents hydrogen or a monovalent hydrocarbon group),

R ¹ and R ² each independently represent hydrogen, a monovalent hydrocarbon group or the following formula (III),

In the formula, X ³ and X ⁴ each independently represent a single bond, O or NR ⁵ (in the formula, R ⁵ represents hydrogen or a monovalent hydrocarbon group), W represents a spacer, and R ⁴ represents hydrogen or a monovalent hydrocarbon group.

In one aspect, (a) the 2-methylene-1,3-dicarbonyl compound is represented by the following formula (IV),

In the formula,

R ¹ and R ² each independently represent hydrogen, a monovalent hydrocarbon group, or the following formula (V),

In the formula, W represents a spacer group, and R ⁴ represents hydrogen or a monovalent hydrocarbon group.

In other aspects, (a) the 2-methylene-1,3-dicarbonyl compound is a dicarbonylethylene derivative represented by the following formula (VI),

In the formula, R ¹¹ is a 1,1-dicarbonylethylene unit represented by the following formula (VII),

Each R ¹² independently represents a spacer group,

R ¹³ and R ¹⁴ each independently represent hydrogen or a monovalent hydrocarbon group,

X ¹¹ and each of X ¹² and X ¹³ independently represent a single bond, O or NR ¹⁵ (in the formula, R ¹⁵ represents hydrogen or a monovalent hydrocarbon group),

Each m independently represents 0 or 1,

n represents an integer from 1 to 20.

In this specification, a monovalent hydrocarbon group refers to a group produced by removing one hydrogen atom from a carbon atom of a hydrocarbon. Examples of the monovalent hydrocarbon group include alkyl, alkenyl, alkynyl, cycloalkyl, alkyl-substituted cycloalkyl, aryl, aralkyl, and alkaryl. Part of it contains heteroatoms such as N, O, S, P and Si. The monovalent hydrocarbon group partially containing heteroatoms may have a polyether structure or a polyester structure, for example.

The aforementioned monovalent hydrocarbon groups can be separated by alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, allyl, alkoxy, alkylthio, hydroxyl, nitro, amide group, azide group, Substituted by cyano group, acyloxy group, carboxyl group, triylene group, acryloxy group, siloxy group, epoxy group, or ester.

The aforementioned monovalent hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an aryl group, or an alkyl group substituted by a cycloalkyl group, and more preferably an alkyl group, a cycloalkyl group, or an alkyl group substituted by a cycloalkyl group.

The number of carbon atoms in the alkyl group, alkenyl group and alkynyl group (hereinafter collectively referred to as "alkyl group, etc.") is not particularly limited. The carbon number of the aforesaid alkyl group is usually 1 to 18, preferably 1 to 16, more preferably 2 to 12, still more preferably 3 to 10, particularly preferably 4 to 8. Moreover, the carbon number of the said alkenyl group and alkynyl group is usually 2-12, Preferably it is 2-10, More preferably, it is 3-8, Still more preferably, it is 3-7, Especially preferably, it is 3-6. When the alkyl group or the like has a cyclic structure, the number of carbon atoms in the alkyl group or the like is usually 5 to 16, preferably 5 to 14, more preferably 6 to 12, still more preferably 6 to 10. For example, the carbon number of the alkyl group, etc. can be identified by the reverse-phase HPLC, nuclear magnetic resonance method (NMR method), and mass spectrometry.

The structures of the aforementioned alkyl groups and the like are not particularly limited. The alkyl group or the like may be linear or may have a side chain. The aforementioned alkyl group, etc. may have a chain structure or a cyclic structure (cycloalkyl group, cycloalkenyl group, and cycloalkynyl group). The above-mentioned alkyl group, etc. may have one type or two or more types of other substituents. For example, the alkyl group mentioned above may have "a substituent containing atoms other than carbon atoms and hydrogen atoms" as a substituent. In addition, the aforementioned alkyl group or the like may contain one or more atoms other than carbon atoms and hydrogen atoms in a chain structure or a cyclic structure. Examples of the atoms other than carbon atoms and hydrogen atoms include one or more of oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and silicon atoms.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, pentyl, and isopentyl. , neopentyl, hexyl, heptyl, octyl, and 2-ethylhexyl. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, and 2-methylcyclohexyl. Examples of the alkenyl group include vinyl, allyl, and isopropenyl. Specific examples of the cycloalkenyl group include cyclohexenyl group.

When (a) the 2-methylene-1,3-dicarbonyl compound is represented by the aforementioned formula (II) or (IV) and both R ¹ and R ² are monovalent hydrocarbon groups, particularly preferably R ¹ and R ² is an alkyl group, cycloalkyl group, alkyl-substituted cycloalkyl group, aryl group, aralkyl group or alkaryl group having 2 to 8 carbon atoms.

In this specification, the spacer group refers to a divalent hydrocarbon group, more specifically, a cyclic, linear or branched substituted or unsubstituted alkylene group. The number of carbon atoms in the alkylene group is not particularly limited. The carbon number of the aforementioned alkylene group is usually 1 to 12, preferably 2 to 10, more preferably 3 to 8, and still more preferably 4 to 8. Here, the aforementioned alkylene group may include "a group containing a heteroatom selected from N, O, S, P and Si" in the middle if necessary. Moreover, the said alkylene group may have an unsaturated bond. In one aspect, the spacer group is an unsubstituted alkylene group having 4 to 8 carbon atoms. The spacer is preferably a linear substituted or unsubstituted alkylene group, and more preferably has the formula -(CH ₂ ) _n - (in the formula, n is an integer from 2 to 10, preferably from 4 to 8) The structure shown is an alkylene group, and the carbon atoms at both ends thereof are bonded with the remaining portion of (a) 2-methylene-1,3-dicarbonyl compound.

Specific examples of the divalent hydrocarbon group as the spacer group include, but are not limited to, 1,4-n-butylene group and 1,4-cyclohexylene dimethylene group.

When the (a) 2-methylene-1,3-dicarbonyl compound has a spacer, the number of carbon atoms of the terminal monovalent hydrocarbon group is preferably 6 or less. That is, when the (a) 2-methylene-1,3-dicarbonyl compound is represented by the aforementioned formula (II) or (IV), R ⁴ in the aforementioned formula (III) or (V) is preferably It is an alkyl group with a carbon number of 1 to 6, but when one of R ¹ and R ² is represented by the aforementioned formula (III) or formula (V), the other of R ¹ and R ² is preferably a carbon number Alkyl groups from 1 to 6. At this time, in the aforementioned formula (II) or (IV), both R ¹ and R ² may be represented by the aforementioned formula (III) or formula (V), but preferably only one of R ¹ and R ² is Those represented by the aforementioned formula (III) or formula (V). Preferably, (a) the 2-methylene-1,3-dicarbonyl compound is represented by the aforementioned formula (IV).

Particularly preferred compounds having a spacer group include: a compound in which one of R ¹ or R ² in the aforementioned formula (IV) is any one of ethyl, n-hexyl or cyclohexyl, and the other is As shown in the aforementioned formula (V), W is either 1,4-n-butylene or 1,4-cyclohexyldimethylene, and R ⁴ is any one of ethyl, n-hexyl, or cyclohexyl. By. In addition, other particularly preferred compounds include: a compound in which R ¹ and R ² in the aforementioned formula (IV) are represented by the aforementioned formula (V), and W is 1,4-n-butyl or 1,4- Any one of cyclohexyl dimethylene, R ⁴ is any one of ethyl, n-hexyl or cyclohexyl.

Various (a) 2-methylene-1,3-dicarbonyl compounds can be synthesized by methods disclosed in patent publications such as WO 2012/054616, WO 2012/054633 and WO 2016/040261. (a) When both ends of the structural unit represented by the aforementioned formula (I) contained in the 2-methylene-1,3-dicarbonyl compound are bonded to oxygen atoms, it can be obtained by using Japanese Patent No. 2015-518503 Conventional methods such as transesterification with diols or polyols disclosed in the publication are used to produce (a) with a larger molecular weight in which a plurality of structural units represented by the aforementioned formula (I) are bonded via ester bonds and the aforementioned spacer groups. )2-methylene-1,3-dicarbonyl compound. In the (a) 2-methylene-1,3-dicarbonyl compound produced in this way, R ¹ and R ² in the aforementioned formula (II) or the aforementioned formula (IV), the aforementioned formula (III) or R ⁴ in the aforementioned formula (V), and R ¹⁴ and R ¹³ in the aforementioned formula (VI) may contain a hydroxyl group. The (a) 2-methylene-1,3-dicarbonyl compound can be obtained by appropriately blending the (a) 2-methylene-1,3-dicarbonyl compound. In particular, polyfunctional components (that is, those belonging to (a) 2-methylene-1,3-dicarbonyl compound and having two or more structural units of the aforementioned formula (I)) can be, for example, based on Japanese Patent Table 2015- It was synthesized by the method disclosed in Publication No. 517973.

Specific examples of preferred (a) 2-methylene-1,3-dicarbonyl compounds include: dibutyl methylene malonate, dipyl methylene malonate, and methylene malonate. Dihexyl methylene malonate, dicyclohexyl methylene malonate, ethyl octyl methylene malonate, propyl hexyl methylene malonate, methylene malonate (2-ethylhexyl ) ester ethyl ester, methylene malonate ethylphenyl ethyl ester, etc. These are preferred because of their low volatility and high reactivity. From the viewpoint of handleability, dihexyl methylene malonate and dicyclohexyl methylene malonate are particularly preferred.

(b) (Meth)acrylate polymer

The liquid polymerizable composition of the present invention contains (b) (meth)acrylate polymer. (b) The (meth)acrylate polymer contains more than one repeating unit represented by the formula -(CH ₂ -CR ^a R ^b )-, where R ^a represents a hydrogen atom or a methyl group, and R ^b represents the formula -C(O)OR ^c represents an alkoxycarbonyl group, and R ^c represents an alkyl group having 1 to 6 carbon atoms. The (b) (meth)acrylate polymer may contain only one type of the above-mentioned repeating units (in this case, the (b)(meth)acrylate polymer is a homopolymer), or may contain two or more types of the above-mentioned repeating units. ((b) (meth)acrylate polymer in this case is a copolymer). However, when it contains only one of the aforementioned repeating units, R ^a and R ^c are not methyl groups at the same time. (b) The (meth)acrylate polymer can be used alone or in combination of two or more types.

(b) (Meth)acrylate polymer is a polymer obtained by polymerizing one or more (meth)acrylic acid alkyl esters (C ₁ to C ₆ alkyl esters of (meth)acrylic acid), (b) ( The aforementioned repeating unit in the methacrylate polymer is derived from "alkyl (meth)acrylate which is a monomer used in the manufacture of (b) (meth)acrylate polymer". For example, if R ^a is methyl and R ^c is ethyl, the repeating unit is derived from ethyl methacrylate. (b) The (meth)acrylate polymer may contain only the aforementioned repeating units derived from alkyl acrylate (C ₁ to C ₆ alkyl ester of acrylic acid), or may contain only alkyl methacrylate (methacrylic acid alkyl ester). The aforementioned repeating units (C ₁ to C ₆ alkyl ester of acrylic acid) may also include combinations of these repeating units.

The structure of the aforementioned alkyl group ^Rc may be chain (linear or branched) or cyclic. The above-mentioned alkyl group, etc. may have one type or two or more types of other substituents. For example, the aforementioned alkyl group may have "a substituent containing atoms other than carbon atoms and hydrogen atoms" as a substituent. Furthermore, the alkyl group may contain one or more atoms other than carbon atoms and hydrogen atoms in a chain structure or a cyclic structure. Examples of the atoms other than carbon atoms and hydrogen atoms include one or more of oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms and silicon atoms.

In one aspect of the present invention, the alkyl group has no substituent. In another aspect of the present invention, the alkyl group contains a substituent. However, the substituent contained in the aforesaid alkyl group preferably does not have active hydrogen. The reason for this is that the substituent having active hydrogen may adversely affect the reactivity of the (a) 2-methylene-1,3-dicarbonyl compound. In one aspect, the aforesaid alkyl group is not substituted by an amine group, a carboxyl group, a hydroxyl group or a thiol group.

Specific examples of the alkyl group R ^c include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-pentyl, isopentyl base, neopentyl, n-hexyl, isohexyl, cyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, and cyclohexyl, etc.

The alkyl group R ^c is preferably an alkyl group having 1 to 4 carbon atoms, and is more preferably selected from the group consisting of methyl, ethyl, and isobutyl.

In one embodiment, (b) (meth)acrylate polymer is selected from the group consisting of a copolymer of ethyl methacrylate and methyl methacrylate, a homopolymer of ethyl methacrylate, and a homopolymer of ethyl acrylate. One or more of the group consisting of polymers and homopolymers of isobutyl methacrylate. Among these, since the viscosity of the liquid polymerizable composition of the present invention can be effectively increased even at a lower concentration, a copolymer selected from the group consisting of ethyl methacrylate and methyl methacrylate, methyl Homopolymers of ethyl acrylate and at least one of the homopolymers of ethyl acrylate, more preferably selected from the group consisting of copolymers of ethyl methacrylate and methyl methacrylate, ethyl methacrylate One or more species in the group of homopolymers of esters.

Moreover, it is preferable that at least part of the (b) (meth)acrylate polymer is dissolved in the (a) 2-methylene-1,3-dicarbonyl compound. In this case, the viscosity of the liquid polymerizable composition of the present invention can be effectively increased. In one aspect of the present invention, (b) (meth)acrylate polymer is completely dissolved in (a) 2-methylene-1,3-dicarbonyl compound.

The homopolymer of methyl methacrylate is not easily soluble in (a) 2-methylene-1,3-dicarbonyl compound, so it is not suitable for adjusting the viscosity of the liquid polymerizable composition of the present invention. Therefore, when the (b) (meth)acrylate polymer contains only one type of repeating unit, R ^a and R ^c are not methyl groups at the same time.

In one aspect of the invention, in all repeating units constituting the (b) (meth)acrylate polymer, R ^a is methyl. In this case, the (b) (meth)acrylate polymer is a methacrylate polymer.

(b) The (meth)acrylate polymer is commercially available. Alternatively, the (b) (meth)acrylate polymer can be obtained by polymerizing an alkyl (meth)acrylate by a conventional method.

The weight average molecular weight of (b) the (meth)acrylate polymer is preferably 100,000 to 1,000,000, more preferably 200,000 to 750,000, and still more preferably 300,000 to 500,000. (b) When the weight average molecular weight of the (meth)acrylate polymer is less than 100,000, sufficient viscosity may not be imparted. shape. (b) If the weight average molecular weight of the (meth)acrylate polymer exceeds 1,000,000, especially when the liquid polymerizable composition does not contain a thixotropic viscosity reducing agent described below, it will be different from (a) 2-methylene-1, The compatibility of 3-dicarbonyl compounds may be insufficient.

In the present invention, regarding the weight average molecular weight of the (meth)acrylate polymer, when a commercially available (meth)acrylate polymer is used, the value based on the catalog value is used. If there is no catalog value or it cannot be calculated from the catalog value, it can be obtained by gel permeation chromatography.

In one aspect of the present invention, the (b) (meth)acrylate polymer contains repeating units derived from an alkyl methacrylate. Preferably, the (b) (meth)acrylate polymer is methacrylic acid. ester polymer. Thus, the (b) (meth)acrylate polymer (especially the methacrylate polymer) can be easily produced having the above-mentioned preferred weight average molecular weight. In addition, many of these are known to be commercially available and are preferable from the viewpoint of easy availability.

The liquid polymerizable composition of the present invention preferably contains 0.1 to 0.1 to 100 parts by weight of (b) (meth)acrylate polymer based on 100 parts by weight of (a) 2-methylene-1,3-dicarbonyl compound. 20 parts by weight, more preferably 0.1 to 15 parts by weight, further preferably 1 to 10 parts by weight. When the amount of (b) the (meth)acrylate polymer is less than 0.1 part by weight, the viscosity of the liquid polymerizable composition may not be sufficiently increased. (b) When the amount of the (meth)acrylate polymer exceeds 20 parts by weight, stringing may occur in the liquid polymerizable composition. In one aspect of the present invention, the liquid polymerizable composition does not generate strings.

Furthermore, in the liquid polymerizable composition of the present invention, if the content of the (b) (meth)acrylate polymer becomes high, it will be difficult to adjust the viscosity. The reason for this is that the change in viscosity becomes larger relative to the change in content of (b) (meth)acrylate polymer. From this point of view, relative to 100 parts by weight of (a) 2-methylene-1,3-dicarbonyl compound, (b) (meth)acrylate polymer in the liquid polymerizable composition of the present invention The content is preferably less than 10 parts by weight.

Furthermore, the above-mentioned Patent Document 1 also describes the combined use of a 2-methylene-1,3-dicarbonyl compound and a (meth)acrylate polymer. However, the composition described in Patent Document 1 is an adhesive composition. The adhesive composition is usually a semi-solid composition that is adhesive and does not have polymerizability or curability. It is very different in use from the liquid polymerizable composition or curable resin composition in this case. Furthermore, in Patent Document 1, the effect obtained by using a 2-methylene-1,3-dicarbonyl compound and a (meth)acrylate polymer in combination is also very different from this case.

In addition to the above (a) 2-methylene 1,3-dicarbonyl compound and (b) (meth)acrylate polymer, the liquid polymerizable composition of the present invention may optionally contain the following components .

． Inorganic filler

The liquid polymerizable composition of the present invention may further contain an inorganic filler if necessary.

Examples of inorganic fillers include: colloidal silica, hydrophobic silica, fine silica, fumed silica (silica particles) and other silica fillers; calcium carbonate, aluminum oxide, zinc oxide and other metals Oxide, nickel, copper, silver and other metals, glass beads, bentonite, acetylene black, Ketjen black, etc. Among these, silica filler is preferred because it can increase the filling amount. The inorganic filler may be surface-treated with a silane coupling agent or the like. When surface-treated fillers are used, the effect of preventing filler aggregation can be expected. An inorganic filler can be used individually or in combination of 2 or more types.

In addition, the average particle size of the inorganic filler (or the average longest diameter if it is non-spherical) is not particularly limited, so that the filler can be uniformly dispersed in the liquid polymerizable composition and the liquid polymerization can be used. From the viewpoint of excellent injectability when the composition is used as a liquid sealing material such as an adhesive or an underfill, the thickness is preferably 0.001 to 50 μm. Here, the average particle diameter of the inorganic filler can be appropriately determined based on its size using an electron microscope or a dynamic light scattering Nanotrac particle size analyzer.

An inorganic filler capable of imparting thixotropic viscosity-reducing properties to the liquid polymerizable composition of the present invention. Hereinafter, this inorganic filler is called "thixotropic viscosity reducing agent". By adding a thixotropic viscosity reducing agent to the liquid polymerizable composition of the present invention, operability (prevention of dripping, etc.) or physical properties (prevention of bleeding, etc.) can be improved. Inorganic fillers may contain thixotropic viscosity reducing agents.

In one embodiment, the liquid polymerizable composition of the present invention further contains a thixotropic viscosity reducing agent. In other aspects, the liquid polymerizable composition of the present invention contains a thixotropic viscosity reducing agent and an inorganic filler other than the thixotropic viscosity reducing agent. The inorganic filler other than thixotropic viscosity reducing agent is preferably silica.

The inventors found that if a thixotropic viscosity reducing agent is added to the 2-methylene-1,3-dicarbonyl compound, the hardening property of the 2-methylene-1,3-dicarbonyl compound will be reduced and the coagulation will be reduced. The glue time will be prolonged, but if a thixotropic viscosity reducing agent is added to the liquid polymerizable composition of the present invention containing 2-methylene-1,3-dicarbonyl compound and a specific (meth)acrylate polymer , it is not easy to produce such adverse effects on sclerosis.

The thixotropic viscosity reducing agent used in the present invention is not particularly limited, and is preferably synthetic silica. Synthetic silica can be synthesized by any method including dry method and wet method, but fumed silica (silica particles) is preferred. Fumed silica is amorphous silica obtained by hydrolyzing halogenated silane such as silicon tetrachloride in a hydrogen-oxygen flame (dry method).

In addition, the thixotropic viscosity reducing agent can be surface treated with a surface treatment agent (such as polydimethylsiloxane). In the present invention, it is preferable that at least part of the thixotropic viscosity reducing agent undergoes surface treatment. The average particle size of the primary particles of the thixotropic viscosity reducing agent is preferably 5 to 50 nm, more preferably 5 to 40 nm. The average particle size of the primary particles of the thixotropic viscosity reducing agent can be determined from electron micrographs through image analysis.

In the liquid polymerizable composition of the present invention, the thixotropic viscosity reducing agent preferably contains 0 to 30% by weight, more preferably 1 to 20% by weight, particularly preferably, relative to the total weight of the liquid polymerizable composition. It contains 1 to 10% by weight.

Inorganic fillers can be insulating or conductive. The inorganic filler may contain a plurality of fillers. Inorganic fillers can all be insulating properties. When all inorganic fillers are insulating, the content of the inorganic filler (including thixotropic viscosity reducing agent) is preferably 0 to 95 parts by weight relative to 100 parts by weight of all components of the liquid polymerizable composition, more preferably It is 0 to 85 parts by weight, and more preferably 0 to 50 parts by weight. If the amount is 0 to 50 parts by weight, when the liquid polymerizable composition is used as a liquid sealing material such as an underfill, deterioration of the injectability of the liquid polymerizable composition can be avoided. If it is 10 to 95 parts by weight, the linear expansion coefficient of the liquid polymerizable composition can be reduced. Moreover, the inorganic filler may contain a conductive inorganic filler. When the inorganic filler contains a conductive inorganic filler, from the viewpoint of electrical conductivity, the content of the conductive inorganic filler is preferably 50 to 95 parts by weight based on 100 parts by weight of all components of the liquid polymerizable composition. share.

． Stabilizer

The liquid polymerizable composition of the present invention may further contain a stabilizer if necessary.

The stabilizer is used to improve the stability of the liquid polymerizable composition during storage and is added to suppress unexpected polymerization reactions caused by free radicals or alkaline components. Although the probability of 2-methylene 1,3-dicarbonyl compound is low, it may generate free radicals by itself, so the free radicals may cause unexpected radical polymerization reactions. In addition, regarding the 2-methylene 1,3-dicarbonyl compound, an anionic polymerization reaction may occur due to the mixing of a very trace amount of an alkaline component. By adding a stabilizer, this unexpected polymerization reaction caused by free radicals or alkaline components can be inhibited.

Stabilizers may be those known in the art, such as strong acids or radical scavengers. Specific examples of the stabilizer include trifluoromethanesulfonic acid, maleic acid, methanesulfonic acid, difluoroacetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid, and aluminum N-nitroso-N-phenylhydroxylamine. , triphenylphosphine, 4-methoxyphenol, and hydroquinone. Among them, the preferred stabilizer is selected from maleic acid, methane sulfonic acid, aluminum N-nitroso-N-phenylhydroxylamine, and At least one of 4-methoxyphenols. In addition, as the stabilizer, conventional ones disclosed in Japanese Patent Application Laid-Open No. 2010-117545, Japanese Patent Application Laid-Open No. 2008-184514, etc. can be used.

The stabilizer can be used alone or in combination of two or more types.

． Interface treatment agent

The liquid polymerizable composition of the present invention may further contain an interface treatment agent if necessary.

The interface treatment agent is not particularly limited, and a coupling agent can usually be used. The coupling agent has more than two different functional groups in the molecule, one of which is a functional group that chemically bonds with the inorganic material, and the other is a functional group that chemically bonds with the organic material. Since the adhesive contains a coupling agent, the adhesion between the adhesive and the substrate can be improved.

Examples of the coupling agent include, but are not limited to, silane coupling agents, aluminum coupling agents, and titanium coupling agents. One type of coupling agent may be used or two or more types may be used in combination.

The functional groups of the silane coupling agent include, for example: vinyl, epoxy, styrene, methacrylyl, acrylyl, amine, isocyanate, urea, sulfhydryl, sulfur Ether group, isocyanate group, etc.

． Pigments

The liquid polymerizable composition of the present invention may further contain a pigment if necessary.

By containing a pigment, the chromaticity of the liquid polymerizable composition of the present invention can be adjusted. The pigment is not particularly limited, and examples thereof include carbon black, titanium black such as titanium nitride, black organic pigments, mixed-color organic pigments, and inorganic pigments. Examples of black organic pigments include perylene black, aniline black, and the like. Examples of mixed-color organic pigments include those in which at least two pigments selected from the group consisting of red, blue, green, violet, yellow, magenta, cyan, etc. are mixed and pseudo-blackened. Examples of inorganic pigments include graphite, metals and their oxides, composite oxides, sulfide Particles of substances, nitrides, etc. Examples of the metal include titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, and the like. The pigment can be used alone or in combination of two or more kinds. The pigment is preferably carbon black or titanium black.

． Plasticizer

The liquid polymerizable composition of the present invention may further contain a plasticizer if necessary.

The plasticizer can be blended with any conventional plasticizer. Plasticizers can improve formability or adjust glass transition temperature. Plasticizers that have good compatibility and are not easy to bleed out can be used.

Examples of the plasticizer include di-n-butyl phthalate, di-n-octyl phthalate, bis(2-ethylhexyl) phthalate, di-n-decyl phthalate, and phthalate. Phthalate esters such as diisodecyl dicarboxylate; adipate esters such as bis(2-ethylhexyl) adipate and di-n-octyl adipate; bis(2-ethyl sebacate) Sebacate esters such as hexyl) ester and di-n-butyl sebacate; azelaic acid esters such as bis(2-ethylhexyl) azelate; paraffins such as chlorinated paraffin; glycols such as polypropylene glycol ; Epoxy modified vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; phosphates such as trioctyl phosphate and triphenyl phosphate; phosphites such as triphenyl phosphite; adipic acid and 1 , ester oligomers such as the esterification product of 3-butanediol; low molecular weight polymers such as low molecular weight polybutene, low molecular weight polyisobutylene, low molecular weight polyisoprene; rubber softening oil, naphthenic oil and other oils Class etc.

A plasticizer can be used individually or in combination of 2 or more types.

The liquid polymerizable composition of the present invention may contain components other than the above-mentioned components within the scope that does not impair the effects of the present invention, such as flame retardants, ion collectors, defoaming agents, leveling agents, and foam breakers. Agents, organic thixotropic viscosity reducers, solvents, etc.

In addition to the above-mentioned (a) 2-methylene 1,3-dicarbonyl compound and (b) (meth)acrylate polymer, the liquid polymerizable composition of the present invention may contain the above-mentioned components if necessary. . Each component can be used in a form dissolved in a solvent. The liquid polymer of the present invention can be prepared by mixing these ingredients. Compatible composition. Mixing may use conventional equipment. For example, the mixture can be mixed by a conventional device such as a Henschel mixer or a roller mill. The ingredients can be mixed simultaneously, or a portion can be mixed first and the remaining portion can be mixed later.

Regarding (b) (meth)acrylate polymer, in particular, it is sometimes provided commercially as a tablet-like or bead-like solid product, based on (a) 2-methylene 1,3-dicarbonyl compound. Depending on the type of (b)(meth)acrylate polymer, there may be cases where the (b)(meth)acrylate polymer cannot be dissolved only by mixing. In this case, for example, (b) (meth)acrylate polymer is first dissolved in a volatile organic solvent to obtain (b) (meth)acrylate polymer solution, and then the aforementioned (b) (meth)acrylate polymer solution is mixed. (a) 2-methylene-1,3-dicarbonyl compound, thereby preparing a liquid polymerizable composition. When blending the above components other than (a) 2-methylene 1,3-dicarbonyl compound and (b) (meth)acrylate polymer, 2-methylene 1,3- The dicarbonyl compound and/or (meth)acrylate polymer solution may also be added to the obtained liquid polymerizable composition. If necessary, the volatile organic solvent can also be removed from the obtained liquid polymerizable composition. For example, volatile organic solvents can be removed by evaporator distillation.

Various hydrocarbons, ethers, esters, ketones, terpenes, alcohols, and mixed solvents thereof can be used as the above-mentioned volatile organic solvents. Specific examples include toluene, tetrahydrofuran, cyclopentyl methyl ether, and the like. From the viewpoint of volatility and problems caused by residual solvents, cyclopentyl methyl ether is preferred.

The present invention also provides a method for producing the liquid polymerizable composition of the present invention, which method includes the following steps:

Dissolve (b) (meth)acrylate polymer in a volatile organic solvent to obtain (b) (meth)acrylate polymer solution; and

The aforementioned (b) (meth)acrylate polymer solution and (a) 2-methylene-1,3-dicarbonyl compound are mixed.

In one aspect of the present invention, the viscosity of the liquid polymerizable composition at 25°C is 80 to 100,000 mPa. s, preferably 80 to 30,000mPa. s. If the viscosity of the liquid polymerizable composition is within this range, it will not cause inconvenience during bonding or molding and will facilitate filling of gaps. In the present invention, the viscosity of the liquid polymerizable composition is a value measured with an E-type viscometer at 10 rpm.

A curable resin composition can be produced by combining "the liquid polymerizable composition of the present invention containing the above components" and "an alkaline substance". It is expected that the alkaline substance will facilitate the polymerization start reaction when the curable resin composition is cured by the Michael addition reaction. In the present invention, the alkaline substance can be used alone or in combination of two or more kinds.

The present invention also provides a curable resin composition, which contains "the liquid polymerizable composition of the present invention" and "a polymerization initiator containing one or more alkaline substances". In particular, it also provides a one-liquid curable resin. composition.

The alkaline substances used in the present invention usually include organic bases, inorganic bases, or organic metal materials.

Examples of the organic base include amine compounds. The aforementioned amine compound refers to an organic compound having at least one primary amine group, a secondary amine group or a tertiary amine group in the molecule. It may also have two or more of these different levels in the same molecule. Amino group. The amine compound preferably contains a secondary amine group or a tertiary amine group. The amine compound is more preferably a tertiary amine compound. The molecular weight of the above-mentioned amine compound is preferably 100 to 1000, more preferably 100 to 500, still more preferably 110 to 300. When the molecular weight of the amine compound is less than 100, it is highly volatile and may affect surrounding components and cause changes in the physical properties of the cured product.

Examples of inorganic bases include: alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali or alkaline earth metal hydroxides such as lithium carbonate, potassium carbonate, sodium carbonate, etc. Metal carbonates; potassium bicarbonate, sodium bicarbonate and other metal bicarbonates, etc.

Examples of organic metal materials include: butyllithium, tert-butyllithium, phenyllithium and other organic alkali metal compounds and organic copper reagents prepared from them; methylmagnesium bromide, dimethylmagnesium, phenylmagnesium Chlorides and other organic alkaline earth metal compounds and organic copper reagents prepared from them; alkoxides such as sodium methoxide and tert-butylmethoxide; carboxylates such as sodium benzoate, etc.

When a curable resin composition using the liquid polymerizable composition of the present invention is used as an electronic material, if the composition contains an inorganic base or an organic metal material, it may cause unexpected effects on the electrical characteristics of peripheral electrical/electronic circuits. The danger. Therefore, the alkaline substance used in the present invention preferably does not contain alkali metals, alkaline earth metals, transition metal elements, or halogen elements. In other aspects, the alkaline substance used in the present invention is non-ionic.

The alkaline substance used in the present invention is preferably an organic base, and more preferably an amine compound.

In the curable resin composition using the liquid polymerizable composition of the present invention, if the alkaline substance is solid during curing, the reaction will proceed on the surface of the alkaline substance, preventing the reaction from spreading to the entire composition. Therefore the hardening will be uneven. Therefore, it is preferable that the alkaline substance is not solid when hardened, that is, it is liquid or soluble in the liquid polymerizable composition.

In the present invention, the alkaline substance may be "one that becomes inactive by latent state and is activated by any stimulus such as heat, light, mechanical shearing, etc." More specifically, the alkaline substance can be a latent hardening catalyst such as microcapsules, ion dissociation type, inclusion type, etc., or it can be an alkali generated by heat, light, electromagnetic waves, ultrasonic waves, or physical shearing. form. The present invention also provides a curable resin composition (especially a one-liquid curable resin composition), which contains "the liquid polymerizable composition of the present invention" and "contains one or more latent alkaline substances." polymerization initiator".

In addition, the "liquid polymerizable composition of the present invention" can also be used as the main agent and combined with a "hardening agent containing an alkaline substance" to provide a "two-liquid mixed curable resin composition" (Adhesive)" set to use. That is, the present invention also provides a kit, which includes:

(A) The main agent containing the liquid polymerizable composition of the present invention; and

(B) Hardener containing alkaline substances.

The kit for providing a two-liquid mixed curable resin composition according to the present invention can be cured by bringing the aforementioned main agent into contact with a curing agent.

In the present invention, the amount of the basic substance used is preferably 0.01 relative to the total amount (100 mol%) of (a) 2-methylene-1,3-dicarbonyl compound in the liquid polymerizable composition. mol% to 30 mol%, preferably 0.01 mol% to 10 mol%. If the amount of the alkaline substance is less than 0.01 mol%, the hardening will be unstable. On the contrary, if the amount of the alkaline substance exceeds 30 mol%, a large amount of alkaline substance that has not formed a chemical bond with the resin matrix will remain in the cured product, which may cause the physical properties of the cured product to decrease or bleed out.

The liquid polymerizable composition of the present invention and the curable resin composition and kit using the liquid polymerizable composition of the present invention can be used as an adhesive or sealing material. In particular, the one-component curable resin composition can be used as a one-component adhesive or sealing material. In addition, it can be used as a solvent-free liquid curable resin composition, a solvent-free liquid adhesive or a sealing material. Specifically, the above-mentioned liquid polymerizable composition, curable resin composition and set are suitable as adhesives or sealing materials for electronic parts. More specifically, the above-mentioned liquid polymerizable composition, curable resin composition and set can be used for bonding and sealing parts for camera modules, and are particularly suitable for bonding sensor modules such as image sensor modules. The present invention also provides an electronic component bonded using the above-mentioned liquid polymerizable composition or a curable resin composition or set using the liquid polymerizable composition. Furthermore, an electronic component sealed using the above-mentioned liquid polymerizable composition, curable resin composition or set is also provided. Also, go up The liquid polymerizable composition and the curable resin composition can be used as an insulating composition or a conductive composition.

The present invention also provides a cured product obtained by curing the liquid polymerizable composition of the present invention or a curable resin composition or set using the liquid polymerizable composition of the present invention in the above manner. Furthermore, a semiconductor device containing the hardened material is also provided.

For example, a jet distributor, a gas distributor, etc. can be used to supply the curable resin composition to the bonded surface. The above-mentioned curable resin composition can be cured at room temperature without heating. In addition, the above-mentioned curable resin composition can be cured by heating at a temperature of 25 to 80° C., for example. The heating temperature is preferably 50 to 80°C. The heating time is, for example, 0.01 to 4 hours.

(Example)

Examples and comparative examples of the present invention will be described below, but the present invention is not limited to these. In addition, in the following Examples and Comparative Examples, "parts" and "%" mean "parts by mass" and "% by mass" unless otherwise specified.

The raw materials of the liquid polymerizable composition used in the Examples and Comparative Examples are as follows.

． (a) 2-methylene-1,3-dicarbonyl compound

In Examples and Comparative Examples, the compounds used as (a) 2-methylene-1,3-dicarbonyl compound are as follows.

(a-1) Dihexyl methylenemalonate (DHMM) (manufactured by SIRRUS Corporation).

(a-2) Dicyclohexyl methylenemalonate (DCHMM) (manufactured by SIRRUS Corporation).

(a-3) Polyfunctional methylene malonate (synthesized by the method described in Example 2 of Japanese Patent Publication No. 2015-517973).

． (b) (Meth)acrylate polymer

In Examples and Comparative Examples, the compounds used as (b) (meth)acrylate polymer are as follows.

(b-1) Homopolymer of ethyl methacrylate (trade name: Hi-pearl M-5001, manufactured by Negami Industrial Co., Ltd., weight average molecular weight: 400,000).

(b-2) Copolymer of ethyl methacrylate and methyl methacrylate (trade name: Hi-pearl D-2546MEL, manufactured by Negami Industrial Co., Ltd., weight average molecular weight: 400,000, ethyl methacrylate and methyl methacrylate Mol ratio of base methyl acrylate: 6/4).

(b-3) Homopolymer of isobutyl methacrylate (product number: W01POS02452, manufactured by Polysciences, Inc., weight average molecular weight: 247,000).

(b-4) Homopolymer of isobutyl methacrylate (product number: 181544-250, manufactured by Sigma-Aldrich JAPAN Contract Co., Ltd., weight average molecular weight: 70,000).

(b-5) Copolymer of ethyl methacrylate and methyl methacrylate (trade name: Hi-pearl M-4501, manufactured by Negami Industrial Co., Ltd., weight average molecular weight: 1,000,000).

． (b’) (Meth)acrylate polymer other than the above (b)

(b'-1) Homopolymer of methyl methacrylate (trade name: Hi-pearl D-250ML, manufactured by Negami Industrial Co., Ltd., weight average molecular weight: 300,000).

． (c)Thixotropic viscosity reducer

In Examples and Comparative Examples, the compounds used as (c) thixotropic viscosity reducing agent are as follows.

(c-1) Surface-treated fumed silica (trade name: AEROSIL (registered trademark) R805, manufactured by Japan AEROSIL Co., Ltd., average particle size 12 nm, surface-treated with octylsilane).

(c-2) Surface-treated fumed silica (trade name: AEROSIL (registered trademark) RY-200, manufactured by Japan AEROSIL Co., Ltd., average particle size 12 nm, surface-treated with polysiloxane oil).

． (d)Alkaline substances

In the Examples and Comparative Examples, the compounds used as (d) the basic substance are as follows.

(d-1) Triethylamine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., molecular weight: 101.19).

(d-2) N,N-dimethylbenzylamine (DMBA, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., molecular weight: 135.21).

[Prepare a solution containing polymer]

According to the following method, a solution in which (b) (meth)acrylate polymer is dissolved in (a) 2-methylene-1,3-dicarbonyl compound is prepared, which is used to prepare a liquid polymerizable composition object person.

Production Example 1: Solution of (a-1) of (b-1)

In an eggplant-shaped flask, 5.00 g of (b-1) was added to 40 g of cyclopentyl methyl ether, stirred with a magnetic stirrer at room temperature, and completely dissolved. 45.0 g of (a-1) was added in small amounts gradually to the obtained solution, and cyclopentyl methyl ether was distilled off from the obtained mixture under reduced pressure to obtain (b-1) (a-1) solution ((b- 1) Concentration: 10% by weight).

Production Example 2: Solution (a-1) of (b-2)

In an eggplant-shaped flask, 1.00 g of (b-2) was added to 10 g of cyclopentyl methyl ether, stirred with a magnetic stirrer at room temperature, and completely dissolved. 9.0 g of (a-1) was added in small amounts gradually to the obtained solution, and cyclopentyl methyl ether was distilled off from the obtained mixture under reduced pressure to obtain (b-2) (a-1) solution ((b- 2) Concentration: 10% by weight).

Production Example 3: Solution (a-1) of (b-3)

Except using (b-3) instead of (b-2), repeat the same operation as Production Example 2, and obtain the concentration of (a-1) solution ((b-3) of (b-3): 10 weight%).

Production Example 4: Solution (a-1) of (b-4)

Except using (b-4) instead of (b-2), repeat the same operation as Production Example 2 to obtain the concentration of (a-1) solution ((b-4) of (b-4): 10 weight%).

Production Example 5: Toluene solution of (b-5)

In a glass container, 30 mg of (b-5) was added to 1 mL of toluene, stirred at room temperature and completely dissolved, to obtain a toluene solution of (b-5).

Comparative manufacturing example 1

Use (a-1) directly.

Comparative manufacturing example 2

Use (a-2) directly.

Comparative Production Example 3: Solution of (a-1) of (b’-1)

In an eggplant-shaped flask, add 1.00g of (b’-1) to 10g of toluene, stir with a magnetic stirrer at room temperature and dissolve completely. To the obtained solution, 4.0 g of (a-1) was added gradually in small amounts, and toluene was distilled off from the obtained mixture under reduced pressure. At this time, a large amount of precipitates were generated. Therefore, the (a-1) solution of (b'-1) (content of (b'-1): 20% by weight) could not be obtained.

Comparative Production Example 4: Solution (a-2) of (b’-1)

In an eggplant-shaped flask, add 1.00g of (b’-1) to 10g of toluene, stir with a magnetic stirrer at room temperature and dissolve completely. To the obtained solution, 4.0 g of (a-2) was added gradually in small amounts, and toluene was distilled off from the obtained mixture under reduced pressure. At this time, a large amount of precipitates were generated. Therefore, the (a-2) solution of (b'-1) (content of (b'-1): 20% by weight) could not be obtained.

Comparative Production Example 5: Solution (a-1) of (b-5)

In an eggplant-shaped flask, 2.28 g of (a-1) was gradually added in small amounts to the solution of Production Example 5 (total amount: about 1 mL) containing 30 mg of (b-5), and toluene was distilled off from the resulting mixture under reduced pressure. , at this time part of (b-5) precipitates. Therefore, the solution of (a-1) of (b-5) cannot be obtained.

[Masterbatch for preparing thixotropic viscosity reducer]

According to the following method, a dispersion (masterbatch) in which (c) thixotropic viscosity reducing agent is dispersed in (b) (meth)acrylate polymer is prepared, which is used to prepare a liquid polymerizable composition By.

Production Example 6: (c-1) (a-1) dispersion

(c-1) was dispersed in (a-1) using a three-roller mill to obtain a masterbatch (content of (c-1): 17% by weight).

Production Example 7: (c-2) (a-1) dispersion

(c-2) was dispersed in (a-1) using a three-roller mill to obtain a masterbatch (content of (c-2): 17% by weight).

[Preparation of liquid polymerizable composition]

Examples 1 to 8 and 10 to 14, Comparative Examples 1 to 13

According to the blending shown in Table 1, if necessary, a liquid polymerizable composition was prepared using those previously prepared in the above-mentioned production examples and comparative production examples. In addition, Comparative Examples 1 and 2 are single compounds unless unexpectedly mixed impurities are taken into account, but they are called "liquid polymerizable compositions" here for convenience. In Table 1, the amount of each component is expressed by weight (unit: g).

In Example 9, a liquid polymerizable composition was prepared in the following manner.

Example 9

The solution of Production Example 5 and the dispersion liquid of Production Example 7 were mixed in amounts corresponding to "the respective desired amounts of (b-5) and (c-2)". To the obtained mixture, (a-1) is added such that (a-1) reaches a desired content. Toluene was distilled off from the obtained mixture under reduced pressure to obtain a liquid polymerizable composition as a viscous dispersion.

In the Examples and Comparative Examples, the characteristics of the liquid polymerizable composition were measured in the following manner.

[Viscosity of liquid polymerizable composition at 25°C]

For the liquid polymerizable composition produced, an E-type viscometer (TVE-25H: manufactured by Toki Industrial Co., Ltd., rotor name: 3°×R9.7) was used, and the temperature was measured at 25℃±2℃, 50%RH± Under the environment of 10%RH, measure the viscosity (unit: mPa.s) in the preset appropriate range (H, R, or U) at 10 revolutions/minute (10rpm) and 1 revolution/minute (1rpm). The results are presented in Table 1.

In addition, regarding the liquid polymerizable compositions of Comparative Examples 1 and 2 (only (a-1) and only (a-2), respectively) and the liquid polymerizable compositions of Comparative Examples 11 and 13, respectively, It has a low viscosity below the measurement limit of the viscometer, so it cannot be measured according to the above method (shown as "BML" in Table 1). According to the technical data sheet of SIRRUS Company, it can be seen that the viscosity of Comparative Example 1 is 5 to 10 mPa. s (25℃), the viscosity of Comparative Example 2 did not reach 50mPa. s(25℃).

[Evaluation of hardening properties of liquid polymerizable compositions]

In a polypropylene microcentrifuge tube, measure 0.50g of the liquid polymerizable composition of each example and comparative example, and add (d-1) triethylamine (12.3 μL) or (d- 2) DMBA (13.1 μL) and mix quickly, and measure the time until the resulting mixture substantially loses fluidity (gel time, unit: minutes). The results are presented in Table 1.

"Substantially losing fluidity" means that the contents in the microcentrifuge tube have become highly viscous and cannot be stirred with a polypropylene stirring rod.

[Table 1-1]

[Table 1-2]

(Inspection of results)

The liquid polymerizable composition of the present invention, which combines and contains (b) (meth)acrylate polymer and (a) 2-methylene-1,3-dicarbonyl compound, has an appropriate viscosity and exhibits Good hardenability (Examples 1 to 14).

The liquid polymerizable composition of the present invention containing a large amount of (b) (meth)acrylate polymer may easily cause stringing depending on the type of (b) (meth)acrylate polymer. In fact, in Example 3, stringing of the liquid polymerizable composition was observed, but in Example 6, stringing was not observed.

In contrast, liquid polymerizable compositions that did not satisfy the requirements of the present invention had insufficient viscosity or curability (Comparative Examples 4 to 13). For example, even if it is a liquid polymerizable composition obtained by combining only (c) a thixotropic viscosity reducing agent with (a) 2-methylene-1,3-dicarbonyl compound, the viscosity rises appropriately, but The curable resin composition prepared using this composition had an adverse effect on the curability and significantly prolonged the gel time (Comparative Examples 7 to 10 and 12). The prolongation of the gel time can be suppressed by using a combination of (c) thixotropic viscosity reducing agent and (b) (meth)acrylate polymer (Examples 7, 8, 10, 11, and 13) .

Although attempts were made to dissolve (b'-1), which is a homopolymer of methyl methacrylate, in (a) 2-methylene-1,3-dicarbonyl compound, it still precipitated and methyl methacrylate could not be prepared. Solutions of ester homopolymers (Comparative Examples 3 and 4). Therefore, (b'-1) cannot be used to obtain a liquid polymerizable composition having an appropriate viscosity and showing good hardening properties.

Furthermore, for example, if 0.1 to 20 parts by weight of (b) (meth)acrylate polymer having an appropriate weight average molecular weight is added to 100 parts by weight of (a) 2-methylene-1,3-dicarbonyl compound, In this way, a liquid polymerizable composition with appropriate viscosity can be obtained (Example 6). On the other hand, even if the above-mentioned amount of (meth)acrylate polymer with a weight average molecular weight of less than 100,000 is added to (a) 2-methylene-1,3-dicarbonyl compound, the liquid state cannot be sufficiently improved. Viscosity of the polymerizable composition (Comparative Example 5). but (b) If the (meth)acrylate polymer has a high molecular weight (for example, about 1,000,000), it will precipitate from the (a) 2-methylene-1,3-dicarbonyl compound and cannot maintain uniform dispersion. Therefore, a liquid polymerizable composition having appropriate viscosity and good curability could not be obtained (Comparative Example 6). On the other hand, when (b) (meth)acrylate polymer and (c) thixotropic viscosity reducing agent are used in combination, a liquid polymerizable composition having appropriate viscosity and good hardening properties can be obtained (Example 9 ).

(Industry Availability)

The liquid polymerizable composition and the curable resin composition of the present invention can impart appropriate viscosity to the 2-methylene-1,3-dicarbonyl compound without impairing the curability, and therefore can be used to manufacture various electronic products. Component.

The entire disclosure content of Japanese Patent Application No. 2022-017010 (filing date: February 7, 2022) is incorporated into this specification by reference.

All documents, patent applications, and technical specifications stated in this specification are hereby incorporated by reference to the same extent as if each individual document, patent application, or technical specification was specifically and individually stated to be incorporated by reference. Instructions.

Claims (11)

A liquid polymeric composition containing: (a) 2-methylene-1,3-dicarbonyl compound having at least one structural unit represented by the following formula (I)

(b) A (meth)acrylate polymer containing one or more repeating units represented by the formula -(CH ₂ -CR ^a R ^b )-, in which R ^a represents a hydrogen atom or a methyl group, and R ^b represents the formula The alkoxycarbonyl group represented by -C(O)OR ^c , R ^c represents an alkyl group with 1 to 6 carbon atoms; however, when it contains only one of the aforementioned repeating units, R ^a and R ^c are not methyl groups at the same time. The liquid polymerizable composition according to claim 1, which contains 0.1 to 20 parts by weight of the (meth)acrylate polymer based on 100 parts by weight of the 2-methylene-1,3-dicarbonyl compound. . The liquid polymerizable composition according to claim 1 or 2, wherein the (meth)acrylate polymer is selected from the group consisting of a copolymer of ethyl methacrylate and methyl methacrylate, and a copolymer of ethyl methacrylate. One or more of the group consisting of homopolymer, homopolymer of ethyl acrylate and homopolymer of isobutyl methacrylate. The liquid polymerizable composition according to any one of claims 1 to 3, wherein at least part of the (meth)acrylate polymer is dissolved in the 2-methylene-1,3-dicarbonyl compound. The liquid polymerizable composition according to any one of claims 1 to 4, further containing a thixotropic agent. A one-liquid curable resin composition comprising: the liquid polymerizable composition according to any one of claims 1 to 5; and a polymerization initiator containing a latent alkaline substance. A kit is used to provide a two-liquid mixed hardening resin composition. The kit includes: (A) A main ingredient containing the liquid polymerizable composition described in any one of claims 1 to 5; and (B) Hardener containing alkaline substances. The liquid polymerizable composition as described in any one of claims 1 to 5, the liquid curable resin composition as described in claim 6, or the set as described in claim 7, is used for Manufacturing electronic parts. A cured product obtained by curing the liquid polymerizable composition according to any one of claims 1 to 5, the liquid curable resin composition according to claim 6, or the set according to claim 7. And the winner. A semiconductor device including the hardened material according to claim 9. A method for producing a liquid polymerizable composition, which is used to produce the liquid polymerizable composition described in any one of claims 1 to 5, and the method includes the following steps: Dissolve (meth)acrylate polymer in a volatile organic solvent to obtain a (meth)acrylate polymer solution; and The (meth)acrylate polymer solution and the 2-methylene-1,3-dicarbonyl compound were mixed.