JP2018193530A - Resin composition - Google Patents

Abstract

To provide a resin composition which can be cured at a low temperature of 80 degrees or less, preferably at room temperature, contains less volatile components during use (application) or curing and is suitable as a single-component adhesive used in producing an image sensor module or an electronic component.SOLUTION: There is provided a resin composition which comprises one or more 2-methylene-1,3-dicarbonyl compounds. At least one of the one or more 2-methylene-1,3-dicarbonyl compounds has a molecular weight of 220 to 10000 and when the whole of the 2-methylene-1,3-dicarbonyl compounds is defined as 1, the weight ratio of the compound having a molecular weight of less than 220 is 0.00 to 0.05. Further, 2-methylene-1,3-dicarbonyl compounds contain a structural unit represented by the following formula (I).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin composition suitable for a one-component adhesive for applications requiring thermosetting at low temperatures, preferably at room temperature. The resin composition of the present invention is used in the manufacture of image sensor modules used as camera modules for mobile phones and smartphones, and electronic components such as semiconductor elements, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and capacitors. It is suitable as a one-component adhesive. In addition, the resin composition of the present invention is expected to be used as a liquid sealing material, an interlayer adhesive film, a prepreg, and the like used when manufacturing a semiconductor device.

At the time of manufacturing an image sensor module used as a camera module for a mobile phone or a smartphone, a one-pack type adhesive that is thermally cured at a temperature as low as possible is used. Even in the production of electronic components such as semiconductor elements, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, capacitors, etc., it is preferable to use a one-component adhesive that is thermally cured at as low a temperature as possible.

In addition, as a characteristic required for a one-component adhesive used when manufacturing an image sensor module and other electronic components, it is also important that there are few components that volatilize during use (during application) or during curing.
When there are many components that volatilize when used at room temperature or during curing, especially when used for electronic parts such as cameras and sensor modules, the volatiles adhere to the sensor, lens, electrode, etc. May cause contamination of electrodes. In general, in a module manufacturing process, cleaning with a solvent may be performed in order to remove contamination generated in the process. If the deposit is in liquid form, it is possible to remove contamination relatively easily by such washing. However, if the deposit is a solid that has hardened on the member, removal from the member becomes difficult. There is a growing concern that production costs will increase, such as a decrease in yield. In addition, when bubbles due to volatile substances are generated in the cured product, the adhesive strength may be reduced due to a decrease in bulk strength or a decrease in adherend interface area. When air bubbles are generated during curing, there is a concern of causing a decrease in reliability, such as the possibility that the positional accuracy of the adherend may decrease due to deformation. In addition, when there are many volatile components, there are concerns about health effects such as irritation to the eyes and bronchi, and the working environment may be deteriorated.

Conventionally, as one-component adhesives for electronic parts such as image sensor modules, thiol-based adhesives, radical initiators and anionic initiators, which contain epoxy resins, polythiol compounds, and curing accelerators as essential components, have been used. An acrylate resin-based adhesive as an essential component is known, and those that can be cured at about 80 ° C. are also known. However, in order to improve production efficiency, a one-component adhesive that can be cured at a lower temperature is demanded.

  Patent Document 1 discloses a resin composition containing diethylmethylene malonate (DEtMM) that can be cured in a short time even at a low temperature such as room temperature. In addition, this document describes that when the substrate has a chemical basic attribute, the resin composition is cured by the base on the substrate surface even if the resin composition does not contain a catalyst. . However, the resin composition of Patent Document 1 has many components that volatilize at the time of normal temperature use or at the time of curing, and particularly when used for electronic component applications such as an image sensor module, adhesion / contamination to sensors, lenses, electrodes, etc. In addition, there is a concern of causing the above-mentioned problems such as deterioration of working environment and deterioration of reliability.

JP-T-2006-506072

  In order to solve the above-mentioned problems of the prior art, the present invention is an image sensor module that can be cured at a low temperature of 80 ° C. or less, preferably at room temperature, and has few components that volatilize during use (application) or curing. Another object of the present invention is to provide a resin composition suitable as a one-pack type adhesive used in the manufacture of electronic parts.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.

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

(1)
A resin composition comprising one or more 2-methylene 1,3-dicarbonyl compounds,
Among the one or more types of 2-methylene 1,3-dicarbonyl compounds, at least one of them has a molecular weight of 220 to 10,000.
When the whole 2-methylene 1,3-dicarbonyl compound is 1, the weight ratio occupied by the molecular weight of less than 220 is 0.00 to 0.05,
The 2-methylene 1,3-dicarbonyl compound is represented by the following formula (I):

The resin composition which is a compound containing the structural unit represented by these.

(2)
The resin composition according to the above item (1), which is substantially free of a 2-methylene 1,3-dicarbonyl compound having a molecular weight of less than 220.

(3)
The resin composition according to the above item (1) or (2), comprising at least one 2-methylene 1,3-dicarbonyl compound containing two or more structural units represented by the formula (I).

(4)
When the entire 2-methylene 1,3-dicarbonyl compound is 1, the weight ratio of the 2-methylene 1,3-dicarbonyl compound containing two or more structural units represented by the above formula (I) is 0. The resin composition according to item (3), which is 0.05 to 0.95.

(5)
The 2-methylene 1,3-dicarbonyl compound is represented by the following formula (II):

(Where
X ¹ and X ² each independently represent a single bond, O or NR ³ (wherein R ³ represents hydrogen or a monovalent hydrocarbon group),
R ¹ and R ² are each independently hydrogen, a monovalent hydrocarbon group or the following formula (III):

(Where
X ³ and X ⁴ each independently represent a single bond, O or NR ⁵ (wherein R ⁵ represents hydrogen or a monovalent hydrocarbon group),
W represents a spacer,
R ⁴ represents hydrogen or a monovalent hydrocarbon group)
The resin composition according to any one of (1) to (4), which is represented by:

(6)
The resin composition according to any one of (1) to (5), further comprising (A) an inorganic filler.

(7)
The resin composition according to any one of (1) to (6), further comprising (B) a curing catalyst.

(8)
Furthermore, the resin composition as described in any one of (1) to (7) above, further comprising (C) a stabilizer.

(9)
The resin composition according to any one of (1) to (8), wherein a weight ratio of the 2-methylene 1,3-dicarbonyl compound to the entire resin composition is 0.01 to 1.00.

(10)
When the whole 2-methylene 1,3-dicarbonyl compound is 1, the weight ratio of those having a vapor pressure of 0.01 mmHg or more at 25 ° C. is 0.00 to 0.05. 9) The resin composition according to any one of the above.

(11)
The resin composition according to any one of (1) to (10), which can be cured by heating.

(12)
Hardened | cured material obtained by hardening | curing the resin composition as described in any one of said item | term (1)-(11).

(13)
An adhesive or a sealing material comprising the resin composition according to any one of (1) to (11) above.

(14)
The adhesive or sealing material according to item (13), which is for electronic parts.

(15)
A film or prepreg comprising the resin composition according to any one of (1) to (11) above.

(16)
The film or prepreg as described in (15) above, which is used for electronic parts.

(17)
A semiconductor device comprising the cured product according to (12), the cured product of the adhesive or the sealing material according to (14), or the cured product of the film or prepreg according to (16).

  Since the resin composition of the present invention can be thermally cured in a short time at a low temperature of 80 ° C. or less, preferably at room temperature, and has few components that volatilize during use (application) or curing, an image sensor module It is suitable as a one-component adhesive used when manufacturing electronic parts. With these characteristics, the manufacturing efficiency of electronic parts can be increased, the contamination to surrounding members is small during use or curing, the work environment can be kept good, and high cured product reliability is obtained. It is also possible.

It is sectional drawing of a camera module.

  The resin composition of the present invention is particularly useful in the case of thermosetting, but even when light, electromagnetic waves, ultrasonic waves, physical shearing, or the like is used as a curing means, it depends on volatilization at normal temperature or reaction heat. Concerns such as volatilization can be reduced, which is useful.

Hereinafter, embodiments of the present invention will be described in detail.

[2-methylene 1,3-dicarbonyl compound]
The 2-methylene 1,3-dicarbonyl compound of the present invention has the following formula (I):

It is a compound containing the structural unit represented by these.
The 2-methylene 1,3-dicarbonyl compound contains one or more structural units of the above formula (I). In some embodiments, the 2-methylene 1,3-dicarbonyl compound has the formula (I) above.
2 or 3 and preferably 2 structural units.

  Since the above-mentioned 2-methylene 1,3-dicarbonyl compound contains the structural unit of the above formula (I), it is typically polymerized by Michael addition in the presence of a base catalyst. It can be used as the main component of the agent. When the above-mentioned 2-methylene 1,3-dicarbonyl compound contains two or more structural units of the above formula (I) (polyfunctional), crosslinking occurs at the time of curing, and the mechanical properties at high temperature of the cured product are improved. Improvements in physical properties are expected.

  The resin composition of the present invention contains one or more 2-methylene 1,3-dicarbonyl compounds, preferably two or more. Among the 2-methylene 1,3-dicarbonyl compounds contained in the resin composition of the present invention, at least one of the compounds has a molecular weight of 220 to 10,000, more preferably 220 to 5000, and still more preferably 220 to 2000. Most preferably, it is 220-1000. When the molecular weight of the 2-methylene 1,3-dicarbonyl compound is less than 220, there is a concern that the vapor pressure at 25 ° C. is too high. On the other hand, when the molecular weight of the 2-methylene 1,3-dicarbonyl compound exceeds 10,000, the viscosity of the resin composition is increased, workability is lowered, and the addition amount of the filler is limited. .

It is preferable that the resin composition of this invention contains a polyfunctional component from a heat resistant viewpoint of hardened | cured material. Here, polyfunctional means that the 2-methylene 1,3-dicarbonyl compound contains two or more structural units of the above formula (I). The number of structural units of the above formula (I) contained in the 2-methylene 1,3-dicarbonyl compound is referred to as “functional group number” of the 2-methylene 1,3-dicarbonyl compound. Among 2-methylene 1,3-dicarbonyl compounds, those having 1 functional group are called “monofunctional”, those having 2 functional groups are called “bifunctional”, and those having 3 functional groups are called “trifunctional”. .
Moreover, it is preferable that the resin composition of this invention does not contain an ester structure from a moisture resistant reliability viewpoint of hardened | cured material.

When the entire 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention is 1, the weight ratio of those having a molecular weight of 220 or more is preferably 0.01 to 1.00, more preferably 0.05 to 1.00.

The resin composition of the present invention can contain a 2-methylene 1,3-dicarbonyl compound having a molecular weight of less than 220. When the entire 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention is 1, the weight ratio of those having a molecular weight of less than 220 is preferably 0.00 to 0.05, more preferably 0.00 to 0.03, more preferably 0.00 to 0.02. Most preferably, the resin composition of the present invention is substantially free of 2-methylene 1,3-dicarbonyl compounds having a molecular weight of less than 220. Here, “substantially free” means that when the whole 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention is 1, the weight ratio of those having a molecular weight of less than 220 is 0.00. It means 00 to 0.01, preferably 0.00 to 0.001. When the content of the 2-methylene 1,3-dicarbonyl compound having a relatively small molecular weight is increased, not only the contamination to peripheral members but also the working environment is deteriorated, the physical properties of the cured product are deteriorated, and the adhesion to the adherend is increased. Concerns such as a decline in power increase.

  The resin composition of the present invention can contain at least one 2-methylene 1,3-dicarbonyl compound containing two or more structural units represented by the above formula (I).

When the whole 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention is defined as 1, the weight ratio of those containing two or more structural units represented by the above formula (I) is preferably 0.01 to 1.00, more preferably 0.05 to 0.95, still more preferably 0.05 to 0.90, particularly preferably 0.10 to 0.90, and most preferably 0.0. 20 to 0.80. In another aspect, when the whole 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention is 1, the weight of one containing two or more structural units represented by the above formula (I) The ratio is 0.00 to 0.10, preferably 0.01 to 0.10. When the whole 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention is defined as 1, the weight ratio of two or more structural units represented by the above formula (I) is 0.01. If it is less than this, sufficient crosslinking is not formed at the time of curing, and the mechanical properties of the cured product at a high temperature (above the softening point) are significantly impaired.

  The weight ratio of the 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention to the entire resin composition is 0.01 to 1.00, more preferably 0.10 to 1.00, More preferably, it is 0.20-1.00. When the weight ratio of the 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention to the entire resin composition is less than 0.1, the 2-methylene 1,3-dicarbonyl compound is a resin composition. There is a concern that curing does not reach the entire product and the curing becomes uneven.

In some embodiments, the 2-methylene 1,3-dicarbonyl compound has the following formula (II):

(Where
X ¹ and X ² each independently represent a single bond, O or NR ³ (wherein R ³ represents hydrogen or a monovalent hydrocarbon group),
R ¹ and R ² are each independently hydrogen, a monovalent hydrocarbon group or the following formula (III):

(Where
X ³ and X ⁴ each independently represent a single bond, O or NR ⁵ (wherein R ⁵ represents hydrogen or a monovalent hydrocarbon group),
W represents a spacer,
R ⁴ represents hydrogen or a monovalent hydrocarbon group)
It is represented by

In some embodiments, the 2-methylene 1,3-dicarbonyl compound has the following formula (IV):

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

(Where
W represents a spacer,
R ⁴ represents hydrogen or a monovalent hydrocarbon group)
It is represented by

In another embodiment, the 2-methylene 1,3-dicarbonyl compound has the following formula (VI):

(Where
R ¹¹ represents the following formula (VII):

Represents a 1,1-dicarbonylethylene unit represented by:
Each R ¹² independently represents a spacer;
R ¹³ and R ¹⁴ each independently represent hydrogen or a monovalent hydrocarbon group,
X ^{11 and} each X ¹² and X ¹³ each independently represent a single bond, O or NR ¹⁵ (wherein R ¹⁵ represents hydrogen or a monovalent hydrocarbon group);
Each m independently represents 0 or 1,
n represents an integer of 1-20.
The dicarbonylethylene derivative represented by these.

  In this specification, the monovalent hydrocarbon group refers to a group in which one hydrogen atom is removed from the carbon atom of the hydrocarbon. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkyl-substituted cycloalkyl group, an aryl group, an aralkyl group, and an alkaryl group. Heteroatoms such as O, S, P and Si may be contained.

The monovalent hydrocarbon groups are alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, allyl, alkoxy, alkylthio, hydroxyl, nitro, amide, azide, cyano, acyloxy, carboxy, sulfoxy, acryloxy, siloxy, epoxy, respectively. Or may be substituted with an ester.
The monovalent hydrocarbon group is preferably an alkyl group substituted with an alkyl group or a hydroxy group, and more preferably an alkyl group.

  The number of carbon atoms of the alkyl group, alkenyl group, and alkynyl group (hereinafter collectively referred to as “alkyl group and the like”) is not particularly limited. Carbon number of the said alkyl group is 1-12 normally, Preferably it is 2-10, More preferably, it is 3-8, More preferably, it is 4-7, Most preferably, it is 5-6. Moreover, carbon number of the said alkenyl group and alkynyl group is 2-12 normally, Preferably it is 2-10, More preferably, it is 3-8, More preferably, it is 3-7, Most preferably, it is 3-6. When the said alkyl group etc. are cyclic structures, carbon number, such as the said alkyl group, is 4-12 normally, Preferably it is 4-10, More preferably, it is 5-8, More preferably, it is 6-8.

  There is no particular limitation on the structure of the alkyl group or the like. The alkyl group or the like may be linear or have a side chain. The alkyl group or the like may have a chain structure or a cyclic structure (a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group). The alkyl group or the like may have one or more other substituents. For example, the alkyl group or the like may have a substituent containing an atom other than a carbon atom and a hydrogen atom as a substituent. Moreover, the said alkyl group etc. may contain 1 or 2 or more atoms other than a carbon atom and a hydrogen atom in a chain structure or a cyclic structure. Examples of the atoms other than the carbon atom and the hydrogen atom include one or more of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.

  Specific examples of the alkyl group include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, Examples include isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, and 2-ethylhexyl group. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a 2-methylcyclohexyl group. Examples of the alkenyl group include a vinyl group, an allyl group, and an isopropenyl group. Specific examples of the cycloalkenyl group include a cyclohexenyl group.

  In the present specification, the spacer refers to a divalent hydrocarbon group, and more specifically, a cyclic, linear or branched substituted or unsubstituted alkylene. The number of carbon atoms of the alkylene is not particularly limited. Carbon number of the said alkylene group is 1-12 normally, Preferably it is 2-10, More preferably, it is 3-8, More preferably, it is 4-7. Here, the alkylene may contain a group containing a heteroatom selected from N, O, S, P, and Si in the middle as desired. In addition, the alkylene may have an unsaturated bond. In some embodiments, the spacer is an unsubstituted alkylene having 4 to 7 carbon atoms.

When the 2-methylene 1,3-dicarbonyl compound has a spacer, the terminal monovalent hydrocarbon group preferably has 3 or less carbon atoms. That is, when the 2-methylene 1,3-dicarbonyl compound is represented by the formula (II) or (IV), R ⁴ in the formula (III) or (V) is an alkyl having 1 to 3 carbon atoms. However, when ^one of R ¹ and R ² is represented by the above formula (III) or formula (V), the other of R ¹ and R ² is alkyl having 1 to 3 carbon atoms. It is preferable. In this case, in the above formula (II) or (IV), both R ¹ and R ² may be represented by the above formula (III) or formula (V), but preferably ^one of R ¹ and R ² Is represented by the above formula (III) or formula (V). Preferably, the 2-methylene 1,3-dicarbonyl compound is represented by the formula (IV).

2-methylene 1,3-dicarbonyl compounds are available from SIRRUS Inc., Ohio, USA. The synthesis method is disclosed in published patent publications such as WO2012 / 054616, WO2012 / 054633, and WO2016 / 040261. When both ends of the structural unit represented by the above formula (I) contained in the 2-methylene 1,3-dicarbonyl compound are bonded to an oxygen atom, the diol or polyol disclosed in JP-T-2015-518503 The structural unit represented by the above formula (I) is bonded in plural via an ester bond and the spacer, by using a known method such as transesterification with 2-methylene 1,3 having a higher molecular weight. -Dicarbonyl compounds can be produced. The 2-methylene 1,3-dicarbonyl compound produced in this way is represented by R ¹ and R ² in the above formula (II) or the above formula (IV), the above formula (III) or the above formula (V). of ^{R 4} and ^{R 14} and ^{R 13} in formula (VI), is, it may include a hydroxy group.

The resin composition of this invention may contain the component described below as needed other than the said 2-methylene 1, 3- dicarbonyl compound.

[(A) component: inorganic filler]
The resin composition of this invention can contain the inorganic filler of (A) component. (A) Component inorganic fillers include silica fillers such as colloidal silica, hydrophobic silica, fine silica and nano silica, metal oxides such as calcium carbonate, alumina and zinc oxide, metals such as nickel, copper and silver, acrylic Examples thereof include beads, glass beads, urethane beads, bentonite, acetylene black, and ketjen black. Among these, silica filler is preferable because the filling amount can be increased. The inorganic filler as the component (A) may be subjected to surface treatment with a silane coupling agent or the like. When a filler that has been subjected to surface treatment is used, an effect of preventing filler aggregation is expected. (A) The inorganic filler of a component may be individual or may use 2 or more types together.

Moreover, the average particle diameter of the inorganic filler of the component (A) (the average maximum diameter in the case where it is not granular) is not particularly limited, but it is 0.01 to 50 μm that the filler is contained in the resin composition. It is preferable for uniform dispersion, and is also preferable for reasons such as excellent injectability when the resin composition is used as a liquid sealing material such as an adhesive or underfill. When it is less than 0.01 μm, the viscosity of the resin composition increases, and there is a possibility that the injectability may deteriorate when used as a liquid sealing material such as an adhesive or underfill. If it exceeds 50 μm, it may be difficult to uniformly disperse the filler in the resin composition. Moreover, from the viewpoint of protecting the copper wire from the thermal stress of the cured resin composition, the average particle size of the component (A) is more preferably 0.6 to 10 μm. As commercial products, high purity synthetic spherical silica manufactured by Admatechs (Product name: SE5200SEE, average particle size: 2 μm; Product name: SO-E5, average particle size: 2 μm; Product name: SO-E2, average particle size: 0.6 μm) And silica manufactured by Tatsumori (product name: FB7SDX, average particle size: 10 μm), silica manufactured by Micron (product name: TS-10-034P, average particle size: 20 μm), and the like. Here, the average particle diameter of the inorganic filler is measured by a dynamic light scattering nanotrack particle size analyzer.

The content of the inorganic filler (A) is preferably 20 to 65 parts by weight, more preferably 30 to 60 parts by weight, even more preferably 100 parts by weight in total of all components of the resin composition. Is 30 to 40 parts by weight. When the resin composition is 30 to 40 parts by weight, when the resin composition is used as a liquid sealing material such as underfill, the linear expansion coefficient of the resin composition can be lowered, and deterioration of injectability can be avoided. .

[(B) component: curing catalyst]
The resin composition of this invention can contain the curing catalyst of (B) component. The (B) component curing catalyst is expected to act as a catalyst when the resin composition is cured by the Michael addition reaction. Although it does not specifically limit as a curing catalyst of (B) component which can be used, For example, acidic catalysts, such as p-toluenesulfonic acid; Amines, such as a triethylamine, a pyridine, and a tributylamine; Imidazole compounds, such as methylimidazole and phenylimidazole; Examples thereof include phosphorus-based catalysts such as triphenylphosphine. In one embodiment, the curing catalyst of component (B) is desirably a base catalyst, and is preferably triethylamine.
(B) The curing catalyst of a component may be individual or may use 2 or more types together.

  The component (B) curing catalyst is a latent curing catalyst such as a microcapsule, an ion dissociation type, an inclusion type, a solid that generates a base or radical by heat, light, electromagnetic waves, ultrasonic waves, physical shearing, or the like. Also good. The resin composition of the present invention can also be used as a two-component adhesive.

   The content of the (B) component curing catalyst is preferably 0.001 to 10 parts by weight with respect to a total of 100 parts by weight of all components of the resin composition, as the amount of the active component such as an amine compound. Preferably it is 0.01-1 weight part, More preferably, it is 0.025-0.50 weight part.

In addition, it can adhere | attach on a base material using the resin composition of this invention. In this case, when the substrate has a chemical basic attribute, the resin composition is cured by the base on the surface of the substrate even if the resin composition does not contain the component (B) curing catalyst. be able to.

[Component (C): Stabilizer]
The resin composition of the present invention may contain (C) a stabilizer.
(C) Stabilizer is for improving the stability of the resin composition during storage, and is added to suppress the occurrence of polymerization reaction due to unintended radicals or basic components. The 2-methylene 1,3-dicarbonyl compound may generate a radical from itself with a low probability, and an unintended radical polymerization reaction may occur based on the radical. In addition, the 2-methylene 1,3-dicarbonyl compound may cause an anionic polymerization reaction by mixing a very small amount of a basic component. (C) By adding a stabilizer, it is possible to suppress the occurrence of a polymerization reaction due to such unintended radicals or basic components.

(C) A well-known thing can be used for a stabilizer, For example, a strong acid and a radical scavenger can be used. Specific examples of the (C) stabilizer include trifluoromethanesulfonic acid, maleic acid, methanesulfonic acid, difluoroacetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid, N-nitroso-N-phenylhydroxylamine aluminum, Mention may be made of phenylphosphine, 4-methoxyphenol and hydroquinone. Among these, a preferred (C) stabilizer is at least one selected from maleic acid, methanesulfonic acid, N-nitroso-N-phenylhydroxylamine aluminum, and 4-methoxyphenol. As the (C) stabilizer, known ones disclosed in JP 2010-117545 A, JP 2008-184514 A, and the like can also be used.
(C) The stabilizer may be used alone or in combination of two or more.

[(D) component: interfacial treatment agent]
The resin composition of the present invention may contain (D) a surface treating agent.
(D) The interfacial treatment agent is not particularly limited, but typically, a coupling agent can be used. The coupling agent has two or more different functional groups in the molecule, one of which is a chemical group that chemically bonds to an inorganic material, and the other one that chemically bonds to an organic material. It is a functional group. When the adhesive contains the coupling agent, the adhesiveness of the adhesive to the substrate or the like is improved.

  Examples of coupling agents include, but are not limited to, silane coupling agents, aluminum coupling agents, titanium coupling agents and the like. A coupling agent may use 1 type and may use 2 or more types together.

Examples of functional groups possessed by silane coupling agents include vinyl groups, epoxy groups, styryl groups, methacryl groups, acrylic groups, amino groups, isocyanurate groups, ureido groups, mercapto groups, sulfide groups, isocyanate groups, etc. Can do.
[(E) component: pigment]
The resin composition of the present invention may contain (E) a pigment.
(E) By including a pigment, the chromaticity of the resin composition of the present invention can be adjusted. (E) Although it does not specifically limit as a pigment, For example, titanium black, such as carbon black and titanium nitride, a black organic pigment, a mixed color organic pigment, an inorganic pigment, etc. can be used. Perylene black, aniline black, etc. as black organic pigments, and pseudo-blackening by mixing at least two kinds of pigments selected from red, blue, green, purple, yellow, magenta, cyan, etc. as mixed color organic pigments Inorganic pigments include graphite and fine metal particles such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, metal oxides, composite oxides, metal sulfides, metals Nitride etc. are mentioned. These may be used alone or in combination of two or more. (E) The pigment is preferably carbon black or titanium black.

[(F) component: plasticizer]
The resin composition of the present invention may contain (F) a plasticizer.
(F) As a plasticizer, well-known arbitrary plasticizers can be mix | blended. (F) With a plasticizer, moldability can be improved and the glass transition temperature can be adjusted. (F) As the plasticizer, those having good compatibility and difficult to bleed can be used.
Examples of (F) plasticizers include phthalates such as di-n-butyl phthalate, di-n-octyl phthalate, bis (2-ethylhexyl) phthalate, di-n-decyl phthalate, diisodecyl phthalate; bis (2-ethylhexyl) ) Adipates such as adipate and di-n-octyl adipate; Sebacates such as bis (2-ethylhexyl) sebacate and di-n-butyl sebacate; Azelaic esters such as bis (2-ethylhexyl) azelate; Chlorination Paraffins such as paraffin; glycols such as polypropylene glycol; epoxy-modified vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; phosphate esters such as trioctyl phosphate and triphenyl phosphate; Rin Esters; ester oligomers such as esterified products of adipic acid and 1,3-butylene glycol; low molecular weight polymers such as low molecular weight polybutene, low molecular weight polyisobutylene, and low molecular weight polyisoprene; process oil, naphthenic oil, etc. Examples thereof include oils.
(F) The plasticizers may be used alone or in combination of two or more.

  The resin composition of this invention contains (A)-(F) component other than the said 2-methylene 1, 3- dicarbonyl compound as needed. The resin composition of the present invention can be prepared by mixing these components. A known apparatus can be used for mixing. For example, it can mix with well-known apparatuses, such as a Henschel mixer and a roll mill. These components may be mixed simultaneously, a part may be mixed first, and the remainder may be mixed later.

[Vapor pressure]
The 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention preferably has a vapor pressure at 25 ° C. of 0.01 mmHg or less. When the entire 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention is 1, the weight ratio of those having a vapor pressure at 25 ° C. of 0.01 mmHg or more is preferably 0.00 to 0.05, more preferably 0.00 to 0.03, and still more preferably 0.00 to 0.01.

  When the resin composition of the present invention is used at a higher temperature, for example, 50 ° C., the 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention has a vapor pressure of 0.5 at 25 ° C. More preferably, it is 001 mmHg or less. In this case, when the whole 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention is 1, the weight ratio of those having a vapor pressure at 25 ° C. of 0.001 mmHg or more is preferably 0. 0.00 to 0.05, more preferably 0.00 to 0.03, and still more preferably 0.00 to 0.01.

  When the resin composition of the present invention is used at a higher temperature, for example, 80 ° C., the 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention has a vapor pressure of 0.5 at 25 ° C. More preferably, it is 0001 mmHg or less. In this case, when the whole 2-methylene 1,3-dicarbonyl compound contained in the resin composition of the present invention is 1, the weight ratio of those having a vapor pressure at 25 ° C. of 0.0001 mmHg or more is preferably 0. 0.00 to 0.05, more preferably 0.00 to 0.03, and still more preferably 0.00 to 0.01.

  The resin composition of the present invention has a vapor pressure at 25 ° C. of 0.01 mmHg or less, more preferably 0.001 mmHg or less, and still more preferably 0.0001 mmHg or less.

  In the present invention, the vapor pressure of a compound such as 2-methylene 1,3-dicarbonyl compound is the value registered in the database of HSPiP (4th Edition 4.1.05), which is commercially available software, and the estimated value by the Y-MB method. Can be based.

  The resin composition of the present invention is a component other than the 2-methylene 1,3-dicarbonyl compound and (A) to (F), for example, a flame retardant, an ion trap agent, and the like, within a range not impairing the effects of the present invention. You may contain an antifoamer, a leveling agent, a foam breaker, etc.

  The resin composition of the present invention can be used as an adhesive or a sealing material. Specifically, the resin composition of the present invention is suitable for adhesion and sealing for electronic components. More specifically, the resin composition of the present invention can be used for parts for camera modules, adhesion and sealing, and is particularly suitable for adhesion of image sensor modules. This is because the resin composition of the present invention has a very small amount of volatile components that contaminate the surroundings, and therefore deposits (solid matter) are less likely to occur.

  For example, as shown in FIG. 1, the resin composition of the present invention can be used for bonding an IR cut filter 20 and a printed wiring board 24. The resin composition of the present invention can be used for adhesion between the image sensor 22 and the printed wiring board 24. The resin composition of the present invention can be used for adhesion between the support 18 and the printed wiring board 24. For supplying the resin composition to the adherend surface, a jet dispenser, an air dispenser, or the like can be used. The resin composition of the present invention can be cured at room temperature without heating. The resin composition of the present invention can also 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, 0.5 to 4 hours.

  The resin composition of the present invention can also be used for image sensor modules other than camera modules. For example, it can be used for adhesion and sealing of components of an image sensor module that may be incorporated in a fingerprint authentication device, a face authentication device, a scanner, a medical device, or the like.

  Moreover, the resin composition of this invention can also be used as a constituent material of a film or a prepreg. In particular, the resin composition of the present invention is suitable for a coverlay film for protecting a wiring pattern, an interlayer adhesive film for a multilayer wiring board, and a constituent material for a prepreg. This is because the resin composition of the present invention has very few volatile components, so that voids are hardly generated. Moreover, the film or prepreg containing the resin composition of the present invention can be preferably used for electronic parts.

  The prepreg containing the resin composition of the present invention can be produced by a known method such as a hot melt method and a solvent method. When the hot melt method is used, the resin composition of the present invention is once coated on a release paper having good releasability from the resin composition without being dissolved in an organic solvent, and then laminated on a sheet-like fiber base material, or a die coater A prepreg can be produced by direct coating or the like. When the solvent method is used, first, the sheet fiber substrate is impregnated with the resin composition varnish by immersing the sheet fiber substrate in a resin composition varnish obtained by dissolving the resin composition of the present invention in an organic solvent. Then, the prepreg can be produced by drying the sheet-like fiber base material.

  The film containing the resin composition of the present invention can be obtained from the resin composition of the present invention by a known method. For example, the resin composition of the present invention is diluted with a solvent to obtain a varnish, which is applied to at least one side of a support and dried, and then provided as a film with a support or a film peeled from the support. be able to.

In the present invention, a cured product obtained by curing the resin composition of the present invention is also provided. Moreover, in this invention, the hardened | cured material obtained by hardening the film or prepreg containing the hardened | cured material obtained by hardening | curing the adhesive agent or sealing material containing the resin composition of this invention, and the resin composition of this invention. Is also provided.
Furthermore, in the present invention, a semiconductor device including the cured product of the present invention, the cured product of the adhesive or the sealing material of the present invention, or the cured product of the film or prepreg of the present invention is also provided.

  In this invention, the resin composition of this invention is apply | coated to the member which comprises an electronic component, and the adhesion method of the member which comprises an electronic component which adheres to the other member which comprises the said electronic component is also provided. The electronic component is preferably a camera module component, and more preferably an image sensor module. Also provided is a method of applying or injecting the resin composition of the present invention to bond or seal an electronic component or a semiconductor element on a substrate. Furthermore, the method of sealing the said electronic circuit is also provided by apply | coating the resin composition of this invention on the electronic circuit formed on the board | substrate.

  Examples of the present invention and comparative examples will be described below. The present invention is not limited to the following examples and comparative examples. In the following examples and comparative examples, the ratio of the components contained in the adhesive is shown in parts by weight.

[Calculation of vapor pressure]
For some embodiments of the 2-methylene 1,3-dicarbonyl compound used in the present invention, the vapor pressure at each temperature was calculated using HSPiP (4th Edition 4.1.05 Y-MB method). Table 1 shows dimethylmethylene malonate (DMeMM), diethylmethylenemalonate (DEtMM), dipropylmethylenemalonate (DPrMM), dibutylmethylenemalonate (DBtMM), dipentylmethylenemalonate (DPeMM), dihexylmethylenemalonate ( The vapor pressure (unit: mmHg) at each temperature for DHeMM), dicyclohexylmethylenemalonate (DCHeMM), and pentanediol diethylmethylenemalonate (PD-XL) is shown. The acrylate resins used for comparison (phenyl acrylate, phenoxyethyl acrylate (PO-A), and dimethylol-tricyclodecane diacrylate (DCP-A)) are also shown in Table 1.

  From Table 1, it can be seen that a 2-methylene 1,3-dicarbonyl compound having a molecular weight of 220 or more has a low vapor pressure, particularly a vapor pressure at 25 ° C. of about 0.01 mmHg or less. A 2-methylene 1,3-dicarbonyl compound having a vapor pressure at 25 ° C. of 0.01 mmHg or less has little volatilization when cured at room temperature, and hardly contaminates surrounding members.

[Adhesive adjustment]
The raw materials of the adhesive used in the following examples and comparative examples are as follows.
2-methylene 1,3-dicarbonyl compound: DEtMM (manufactured by SIRRUS, R ¹ = R ² = C ₂ H ₅ in the above formula (IV)), DHeMM (manufactured by SIRRUS, R ¹ = in the above formula (IV) R ² = n—C ₆ H ₁₃ ), PD-XL (manufactured by SIRRUS, in the above formula (IV), R ¹ = C ₂ H ₅ , R ² = the above formula (V), W = — (CH ₂ ) ₅ −, R ⁴ = C ₂ H ₅ )
(A) Inorganic filler: SE5200SEE (manufactured by Admatech)
(B) Curing catalyst: Triethylamine (manufactured by Wako Pure Chemical Industries)
In Comparative Examples, phenyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), phenoxyethyl acrylate (PO-A, manufactured by Kyoeisha Chemical Co., Ltd.) or dimethylol- Some use tricyclodecane diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.).

  Adhesives were prepared by mixing the 2-methylene 1,3-dicarbonyl compound or acrylate and optionally (A) to (B) components in the mixing ratios shown in Tables 2 and 3. The following properties were measured for the prepared adhesive.

1. Evaluation of adhered matter 0.05 g of an adhesive was placed in an aluminum pan (diameter: 5 mm, height: 5 mm), and a cover glass (18 × 18 mm) was placed so as to cover the entire upper opening. After standing for 12 hours at the curing temperature described in Table 2 or 3, the presence or absence of deposits on the cover glass, and if there are deposits, whether they are liquid or solid, visually and tweezers Confirmed by finger touch.

2. Evaluation of adhesive strength An adhesive was spot-applied on a SUS plate so as to have a diameter of about 2 mm, and a 2 × 1 mm alumina chip was loaded thereon. After leaving at the curing temperature described in Table 2 or 3 for 12 hours, the bond strength was evaluated with a bond tester (Dage, Series 4000) at 25 ° C.

(Consideration of results)
The monofunctional 2-methylene-1,3-dicarbonyl compound DHeMM (Example 1) and the bifunctional PD-XL (Examples 2 and 3) partially cured at 25 ° C. Sufficient adhesive strength was developed. In particular, Examples 2 and 3 containing PD-XL, which is a bifunctional compound, had a higher adhesive strength than Example 1. Also, no obvious deposits were observed in these.

In general, the monofunctional acrylate resin PO-A, which is an acrylate resin widely used as an adhesive, did not cure at 25 ° C. or 80 ° C. and did not exhibit adhesive strength (Comparative Example 1). And 2). In addition, although the obvious deposit was not seen at 25 degreeC, the liquid deposit was confirmed at 80 degreeC.
DCP-A, which is a bifunctional acrylate resin, was not cured at 25 ° C. and did not exhibit adhesive strength (Comparative Example 3).

(Consideration of results)
In the case of blending about 5% by weight of DEtMM, which is a monofunctional 2-methylene-1,3-dicarbonyl compound having a high vapor pressure, no obvious deposit was observed, and sufficient adhesive strength due to curing was expressed (implementation) Example 4).
Even when about 10% by weight or more of DEtMM was blended, sufficient adhesive strength was exhibited by curing, but the cover glass was clearly cloudy in the adhesion evaluation, and the adhesion was solid when touched with tweezers. Was confirmed (Comparative Examples 4 and 5).

DHeMM exhibited sufficient adhesive strength even when the amount of catalyst was reduced, and no deposit was observed (Example 5).
Even when DHeMM contained a filler, sufficient adhesive strength was developed, and no deposit was observed (Examples 6 and 7).

  Phenyl acrylate, which is a monofunctional acrylate resin, was not cured and did not exhibit adhesive strength, and liquid deposits were also confirmed (Comparative Example 6).

  From the above, it was found that acrylate resins that are widely used as adhesives generally do not cure at 25 ° C. and cannot be used as adhesives. Moreover, even if it is an adhesive agent containing a 2-methylene-1,3-dicarbonyl compound, when it does not contain at least one sort whose molecular weight is 220-10000, or the said 2-methylene 1,3-dicarbonyl When the weight ratio of the molecular weight of less than 220 is not 0.00 to 0.05 when the total compound is 1, when the image sensor module or the electronic component is manufactured, the deposit is left around after curing. It was found that it was not suitable for the one-component adhesive used.

That is, the comparative example cannot be cured at a low temperature and / or has a problem of leaving an adhering substance in the surroundings after curing, while only the example of the present invention can be cured at a low temperature and has been cured. Since no deposits are left behind in the surroundings, it is suitable as a one-component adhesive used when manufacturing image sensor modules and electronic components.

DESCRIPTION OF SYMBOLS 10 Camera module 12 Lens 14 Voice coil motor 16 Lens unit 18 Support body 20 Cut filter 22 Image sensor 24 Printed wiring board 30, 32, 34 Adhesive

Claims (17)

A resin composition comprising one or more 2-methylene 1,3-dicarbonyl compounds,
Among the one or more types of 2-methylene 1,3-dicarbonyl compounds, at least one of them has a molecular weight of 220 to 10,000.
When the whole 2-methylene 1,3-dicarbonyl compound is 1, the weight ratio occupied by the molecular weight of less than 220 is 0.00 to 0.05,
The 2-methylene 1,3-dicarbonyl compound is represented by the following formula (I):

The resin composition which is a compound containing the structural unit represented by these.   The resin composition according to claim 1, which is substantially free of a 2-methylene 1,3-dicarbonyl compound having a molecular weight of less than 220.   The resin composition according to claim 1 or 2, comprising at least one 2-methylene 1,3-dicarbonyl compound containing two or more structural units represented by the formula (I).   When the entire 2-methylene 1,3-dicarbonyl compound is 1, the weight ratio of the 2-methylene 1,3-dicarbonyl compound containing two or more structural units represented by the above formula (I) is 0. The resin composition of Claim 3 which is 0.05-0.95. The 2-methylene 1,3-dicarbonyl compound is represented by the following formula (II):

(Where
X ¹ and X ² each independently represent a single bond, O or NR ³ (wherein R ³ represents hydrogen or a monovalent hydrocarbon group),
R ¹ and R ² are each independently hydrogen, a monovalent hydrocarbon group or the following formula (III):

(Where
X ³ and X ⁴ each independently represent a single bond, O or NR ⁵ (wherein R ⁵ represents hydrogen or a monovalent hydrocarbon group),
W represents a spacer,
R ⁴ represents hydrogen or a monovalent hydrocarbon group)
The resin composition as described in any one of Claims 1-4 represented by these.   Furthermore, the resin composition as described in any one of Claims 1-5 containing (A) inorganic filler.   Furthermore, (B) The resin composition as described in any one of Claims 1-6 containing a curing catalyst.   Furthermore, the resin composition as described in any one of Claims 1-7 containing (C) stabilizer.   The resin composition according to any one of claims 1 to 8, wherein a weight ratio of the 2-methylene 1,3-dicarbonyl compound to the whole resin composition is 0.01 to 1.00.   The weight ratio of those having a vapor pressure at 25 ° C of 0.01 mmHg or more when the whole 2-methylene 1,3-dicarbonyl compound is 1, is 0.00 to 0.05. The resin composition according to claim 1.   The resin composition according to claim 1, which can be cured by heating.   Hardened | cured material obtained by hardening | curing the resin composition as described in any one of Claims 1-11.   The adhesive agent or sealing material containing the resin composition as described in any one of Claims 1-11.   The adhesive or sealing material according to claim 13, which is used for electronic parts.   The film or prepreg containing the resin composition as described in any one of Claims 1-11.   The film or prepreg according to claim 15, which is used for electronic parts.   A semiconductor device comprising the cured product according to claim 12, a cured product of the adhesive or sealing material according to claim 14, or a cured product of the film or prepreg according to claim 16.