KR20220134586A - Molded article and its precursor, manufacturing method and use - Google Patents

Abstract

A molded body including a resin and a dielectric filler is manufactured through an aggregation process of applying active energy to a partial region of a liquid precursor including a resin precursor and a dielectric filler to agglomerate the dielectric filler to obtain a precursor molded body. The molded body is formed of an agglomerated portion, which is a region in which the dielectric filler aggregates, and a non-agglomerated portion, which is a region other than the agglomerated portion. is gradually decreasing towards The resin may be a cured product of a photocurable resin. The photocurable resin may be a cationically polymerizable compound. The ratio of the dielectric filler may be 0.1 to 100 parts by mass based on 100 parts by mass of the resin. The molded article may be in the form of a film.

Description

Molded article and its precursor, manufacturing method and use

The present disclosure relates to a molded article having a region in which a dielectric filler aggregates in a resin, a precursor thereof, a manufacturing method, and a use thereof.

Dielectric materials are widely used as passive components such as capacitors (capacitors), resistors, and inductors in electrical and electronic devices because they have a property of causing electrical polarization and storing electricity when a voltage is applied. In addition, dielectric materials used for these purposes are usually in the form of a sheet, and not only mechanical strength and durability are required, but also flexibility is required in many cases in the form of being wound in a roll shape. For this reason, as a dielectric material, a composite dielectric material containing a dielectric filler in a resin has also been developed. In the composite dielectric material, there is a trade-off relationship between electrical and mechanical properties, and the dielectric constant is improved by increasing the ratio of the dielectric filler. When this is done, the mechanical properties of the dielectric material are lowered. In recent years, since the density and miniaturization of electronic components are progressing due to the spread of mobile devices such as smartphones, it is required to improve the relative dielectric constant (high dielectric constant) and to achieve both mechanical properties such as flexibility and the like in composite dielectric materials.

Japanese Patent Application Laid-Open No. 2018-6052 (Patent Document 1) discloses a dielectric composite material in which a film made of a dielectric filler is formed around matrix particles made of a resin, and the dielectric filler forms a three-dimensional network. .

In Japanese Patent Publication No. 6264897 (Patent Document 2), by mixing a resin melt and a dispersion liquid of an inorganic filler dispersed in a dispersion medium, and coating a paint in which the inorganic filler is dispersed in the resin by ultrasonic vibration, the resin in a non-uniform state A high dielectric constant film in which an inorganic filler is dispersed is disclosed.

Patent Document 1: Japanese Patent Laid-Open No. 2018-6052 Patent Document 2: Japanese Patent Publication No. 6264897

However, the dielectric composite material and the high-k film of Patent Documents 1 and 2 are not easy to control the structure, have low simplicity and low productivity, and are not sufficiently high-permittivity. In addition, in patent document 1, it is not easy to manufacture using the parallel model shown in the cross-sectional schematic diagram of FIG. 1 using a small amount of dielectric filler, and it is described as an unrealistic model.

Accordingly, an object of the present disclosure is to provide a method by which a molded article having regions in which dielectric fillers are aggregated in a resin can be easily manufactured.

Another object of the present disclosure is to provide a molded article in which agglomerated regions of a dielectric filler are formed in various shapes or patterns, a precursor thereof, a manufacturing method, and a use thereof.

Another object of the present disclosure is to provide a film-like molded article having a filler aggregation region in a form that crosses or penetrates in the thickness direction, a precursor thereof, a manufacturing method, and a use thereof.

Another object of the present disclosure is to provide a film-like molded article capable of compatibility of mechanical properties such as flexibility (or toughness) and high dielectric constant properties, and a precursor thereof, a manufacturing method, and a use thereof.

Another object of the present disclosure is to provide a film-like molded article capable of improving high dielectric constant characteristics, low dielectric loss and heat resistance, and a precursor thereof, a manufacturing method, and use thereof.

As a result of further intensive studies to achieve the above object, the present inventors have found that if active energy is applied to a partial region of a liquid precursor including a resin precursor and a dielectric filler, the dielectric filler can be aggregated in a specific region, and the dielectric in the resin The present invention was completed by discovering that a molded article having a region in which fillers aggregated could be easily manufactured.

That is, the molded article of the present disclosure includes a resin and a dielectric filler (or dielectric particles), and is formed into an agglomerated portion that is an area in which the dielectric filler aggregates and a non-agglomerated portion that is a region other than the aggregated portion, and at the same time, in the aggregated portion The abundance ratio of the dielectric filler of , at least in the vicinity of the interface with the non-agglomerated portion, gradually decreases toward the interface. The resin may be a cured product of a photocurable resin. The photocurable resin may be a cationically polymerizable compound. The dielectric filler may be an inorganic filler formed of a titanium-containing composite metal oxide. The ratio of the dielectric filler may be 0.1 to 100 parts by mass based on 100 parts by mass of the resin. The molded article may be in the form of a film. The film-like molded body may be formed in a form in which a plurality of agglomerate portions form a pattern shape, and at least one aggregated portion of the plurality of aggregated portions extends in a thickness direction and penetrates therethrough. The molded body may be a dielectric film.

The present disclosure also includes a method for manufacturing the molded body including an aggregation step of applying active energy to a partial region of a liquid precursor including a resin precursor and a dielectric filler to agglomerate the dielectric filler to obtain a precursor molded body. This production method may include a polymerization completion step of imparting active energy to an uncured region of the precursor molded body that has undergone the agglomeration step to complete polymerization. In the manufacturing method, the liquid precursor may contain a photoacid generator, and the active energy may be actinic light. In addition, the present disclosure includes a molded article obtained by the above production method.

The present disclosure provides a liquid precursor for forming a molded article comprising a photocurable resin and a dielectric filler, wherein the molded body has an agglomerated portion that is a region in which the dielectric filler aggregates and a non-agglomerated portion that is a region other than the agglomerated portion, the photocurable resin and Liquid precursors containing dielectric fillers are also included.

The present disclosure also includes a bonded body in which a substrate formed of a resin, ceramic, or metal and the molded body are joined. This junction may be a capacitor.

In the present disclosure, since active energy is applied to a partial region of the liquid precursor including the resin precursor and the dielectric filler, a molded article having a region in which the dielectric filler aggregates in the resin can be manufactured simply (efficiently). In addition, if a desired shape or patterned mask is used, a molded article in which dielectric filler aggregation regions are formed in various shapes or patterns can be manufactured simply or precisely. In addition, a filler aggregation region of a form that is transverse or continuous in the thickness direction (a high dielectric constant structure in which a dielectric is continuous in the thickness direction referred to as a parallel connection model; for example, the structure shown in FIG. 1 described in Patent Document 1, etc.) A film-like (or sheet-like) molded article having For this reason, the dielectric characteristic can be expressed effectively in the thickness direction of a film-shaped molded object. Moreover, since the addition amount of a dielectric filler can provide a dielectric characteristic efficiently at least, mechanical characteristics, such as softness|flexibility (or toughness) of a film-formed object, and a high dielectric constant characteristic can be compatible. In addition, a molded article excellent in high dielectric constant characteristics, low dielectric loss and heat resistance can also be obtained.

1 is a schematic cross-sectional view of a composite material described in Patent Document 1 as not being easy to manufacture.
Fig. 2 is a schematic partial longitudinal sectional view of the sheet-like molded article of the present invention shown for explaining the non-uniformity of the dielectric filler concentration in the agglomeration portion.
Fig. 3 is a view showing the pattern shape of the photomask used in Examples.
Fig. 4 is a view showing another pattern shape of the photomask used in Examples.
5 is a CCD (charge coupled device) photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Comparative Example 1. FIG.
6 is a CCD photograph of the surface of the film obtained in Comparative Example 2 ((a) 100 times, (b) 400 times).
7 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 1. FIG.
8 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 2. FIG.
9 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 3;
10 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 4;
11 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 5. FIG.
12 is a CCD photograph of the surface of the film obtained in Example 6 ((a) 100 times, (b) 400 times).
13 is a CCD photograph of the surface of the film obtained in Example 7 ((a) 100 times, (b) 400 times).
14 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 8. FIG.
15 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 9. FIG.
16 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 10. FIG.
17 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 11. FIG.
18 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 12. FIG.
19 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 13. FIG.
20 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 14. FIG.
21 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 15. FIG.
22 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 16. FIG.
23 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 17. FIG.
24 is a CCD photograph of the surface ((a) 100 times, (b) 400 times) of the film obtained in Example 18. FIG.
25 is a CCD photograph of the surface (100 times) of the film obtained in Comparative Example 4.
Fig. 26 is a CCD photograph of the surface (100 times) of the film obtained in Example 19.
Fig. 27 is a CCD photograph of the surface (100 times) of the film obtained in Example 20.
Fig. 28 is a CCD photograph of the surface (100 times) of the film obtained in Example 21.
29 is a CCD photograph of the surface (100 times) of the film obtained in Comparative Example 5;
Fig. 30 is a CCD photograph of the surface (100 times) of the film obtained in Example 22.
Fig. 31 is a CCD photograph of the surface (100 times) of the film obtained in Example 23.
Fig. 32 is a CCD photograph of the surface (100 times) of the film obtained in Example 24.
Fig. 33 is a CCD photograph of the surface (100 times) of the film obtained in Comparative Example 6.
Fig. 34 is a CCD photograph of the surface (100 times) of the film obtained in Example 25.
Fig. 35 is a CCD photograph of the surface (100 times) of the film obtained in Example 26.
Fig. 36 is a CCD photograph of the surface (100 times) of the film obtained in Example 27.
Fig. 37 is a CCD photograph of the surface (100 times) of the film obtained in Comparative Example 7.
Fig. 38 is a CCD photograph of the surface (100 times) of the film obtained in Example 28.
Fig. 39 is a CCD photograph of the surface (100 times) of the film obtained in Example 29.

[Mold]

The molded article of the present disclosure includes a resin and a dielectric filler, and is a molded article formed of an agglomerated portion, which is a region in which the dielectric filler aggregates, and a non-agglomerated portion (or matrix portion) that is a region other than the aggregated portion. A (composite molded article) is obtained by applying an active energy to a partial region of a liquid precursor including a resin precursor and a dielectric filler to agglomerate the dielectric filler. In the present disclosure, it can be inferred that, in the aggregation step, the resin precursor polymerizes in the region to which the active energy is applied, and the dielectric filler moves along with the polymerization to form the agglomeration portion. The dielectric filler may be moved to a region to which active energy is not applied or may be moved to a region to which active energy is applied, depending on a combination of formulations and selection of manufacturing conditions.

(Suzy)

The resin may be any resin that can be polymerized by active energy, and the resin obtained by polymerization may be a thermoplastic resin.

Examples of the curable resin include a cationically polymerizable compound and/or a radically polymerizable resin. Among these, a cationically polymerizable compound is preferable from points, such as productivity. The cationically polymerizable compound can easily or precisely prepare a desired molded article, perhaps because the reaction rate is suitable for the movement (aggregation) of the dielectric filler. In addition, cationic polymerization can be carried out in the presence of oxygen, such as in air, and furthermore, by using a dark reaction (or post-polymerization) or the like, curability can be easily controlled, so that the productivity is excellent.

The cationically polymerizable compound is not particularly limited as long as it has at least one cationically polymerizable group, and may be a monofunctional cationically polymerizable compound having one cationically polymerizable group, or polyfunctional cationic polymerization having two or more identical or different cationically polymerizable groups. It may be a sexual compound. From the viewpoint of curability and resin strength (or strength of a molded article such as hardness), a polyfunctional cationically polymerizable compound is usually used well. In the case of a polyfunctional cationically polymerizable compound, the number of cationically polymerizable groups can be selected from the range of about 2-10, for example, 2-8 (for example, 2-6), Preferably 2- 4, even more preferably 2-3, especially 2.

Examples of the cationically polymerizable group include an epoxy (oxirane ring)-containing group, an oxetane ring-containing group, and a vinyl ether group.

The epoxy-containing group may be any group having at least an oxirane ring skeleton, for example, an epoxy group (or oxiran-2-yl group), a 2-methyloxiran-2-yl group, a glycidyl-containing group (for example, , glycidyl group, 2-methyl glycidyl group, etc.), alicyclic epoxy group (eg, epoxycycloalkyl group such as 3,4-epoxycyclohexyl group, 3,4-epoxy-6-methylcyclohexyl group, etc.) alkyl-epoxycycloalkyl group, etc.) and the like.

The oxetane ring-containing group may be any group having at least an oxetane ring skeleton, for example, an oxetanyl group (3-oxetanyl group, etc.), an alkyloxetanyl group (eg 3-methyl-3-oxetanyl group). , a C _1-4 alkyloxetanyl group such as a 3-ethyl-3-oxetanyl group), and the like.

You may have these cationically polymerizable groups individually or in combination of 2 or more types. Of these cationically polymerizable groups, epoxy-containing groups such as glycidyl-containing groups and alicyclic epoxy groups are well used from the viewpoints of curability and productivity suitable for aggregation of dielectric fillers.

Representative cationic polymerizable compounds include an epoxy compound having an epoxy-containing group, an oxetane compound having an oxetane ring-containing group, a vinyl ether compound having a vinyl ether group, an epoxy-containing group, an oxetane ring-containing group, and a vinyl ether group. The polyfunctional compound etc. which have a sexual group are mentioned.

These cationically polymerizable compounds may be used individually or in combination of 2 or more types. Among these cationically polymerizable compounds, compounds having at least one cationically polymerizable group selected from the above epoxy-containing groups and oxetane ring-containing groups such as epoxy compounds and oxetane compounds are well used, and among them, compounds having at least an epoxy group are It is preferable, and an epoxy compound is still more preferable from a viewpoint of hardenability suitable for aggregation of a dielectric filler, productivity, etc.

As said epoxy compound, the monofunctional epoxy compound which has one epoxy-containing group as a cationically polymerizable group, and the polyfunctional epoxy compound which has two or more epoxy-containing groups are mentioned. These epoxy compounds may be used individually or in combination of 2 or more types.

As a monofunctional epoxy compound, the monofunctional glycidyl type epoxy compound which has a glycidyl group (or 2-methyl glycidyl group), the monofunctional alicyclic epoxy compound which has an alicyclic epoxy group, etc. are mentioned, for example. Examples of the monofunctional glycidyl type epoxy compound include alkyl glycidyl ethers such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, and tridecyl glycidyl ether; aryl glycidyl ethers such as phenyl glycidyl ether and alkylphenyl glycidyl ether (tolyl glycidyl ether, t-butylphenyl glycidyl ether, etc.); (poly)alkylene glycol monoglycidyl ethers such as ethylene glycol monoglycidyl ether, 1,4-butanediol monoglycidyl ether, and diethylene glycol monoglycidyl ether; 2, 3-epoxy-1-propanol (or glycidol); glycidyl (meth)acrylate; glycidyl oxyalkyl (meth)acrylates such as glycidyl oxyethyl (meth)acrylate; glycidyl oxy (poly) alkoxyalkyl (meth) acrylates such as 2-(2-glycidyl oxyethoxy) ethyl (meth) acrylate; The compound etc. which made the glycidyl group in these compounds a 2-methyl glycidyl group are mentioned.

Examples of the monofunctional alicyclic epoxy compound include 1,2-epoxycyclohexane and substituted epoxycyclohexane (eg, 1,2-epoxy-4-hydroxymethylcyclohexane, 1,2-epoxy-4- vinylcyclohexane, 3,4-epoxy-cyclohexylmethyl (meth)acrylate, allyl-3,4-epoxycyclohexane carboxylate, etc.) and the like.

Examples of the polyfunctional epoxy compound include a polyfunctional glycidyl type epoxy compound having a glycidyl group (and/or a 2-methyl glycidyl group), and a polyfunctional alicyclic epoxy compound having at least one alicyclic epoxy group. can In addition, in the present specification and claims, an epoxy compound having both a glycidyl group and an alicyclic epoxy group is classified as an alicyclic epoxy compound.

As a polyfunctional glycidyl type epoxy compound, for example, a glycidyl ether type epoxy compound (or glycidyl ether type epoxy resin), a glycidyl ester type epoxy compound (or glycidyl ester type epoxy resin), glycidyl ester type epoxy resin A dilamine-type epoxy compound (or a glycidylamine-type epoxy resin), a heterocyclic glycidyl-type epoxy compound, etc. are mentioned.

As a glycidyl ester type epoxy compound, For example, diglycidyl phthalates, such as a diglycidyl phthalate, a diglycidyl tetrahydrophthalate, and a diglycidyl hexahydrophthalate; a homo or copolymer of glycidyl (meth)acrylate; The compound etc. which made the glycidyl group in these compounds a 2-methyl glycidyl group are mentioned.

As a glycidyl amine type epoxy compound, For example, tetraglycidyl diamines, such as tetraglycidyl diamino diphenylmethane, tetraglycidyl metaxylylene diamine, tetraglycidyl bisaminomethyl cyclohexane; Diglycidyl aniline, diglycidyl toluidine, N, N-diglycidyl-2, 4, 6-tribromoaniline, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, etc. of glycidyl anilines; The compound etc. which made the glycidyl group in these compounds a 2-methyl glycidyl group are mentioned.

As a heterocyclic glycidyl type epoxy compound, For example, Isocyanurate type epoxy compounds, such as triglycidyl isocyanurate; hydantoin-type epoxy compounds such as diglycidyl hydantoin; The compound etc. which made the glycidyl group in these compounds a 2-methyl glycidyl group are mentioned.

These polyfunctional glycidyl-type epoxy compounds can also be used individually or in combination of 2 or more types. Among these, a glycidyl ether type epoxy compound is preferable from a viewpoint of hardenability, productivity, etc. suitable for aggregation of a dielectric filler.

Representative examples of the glycidyl ether type epoxy compound include an aromatic glycidyl ether type epoxy compound, an alicyclic glycidyl ether type epoxy compound, and an aliphatic glycidyl ether type epoxy compound.

Examples of the aromatic glycidyl ether type epoxy compound include polyglycidyl ether of an aromatic polyol or an alkylene oxide adduct thereof, and for example, a non- or bisphenol type epoxy compound (eg, a bisphenol A type epoxy compound). , bisphenol F-type epoxy compound, bisphenol AD-type epoxy compound, diglycidyl ether of common bisphenols such as bisphenol S-type epoxy compound, diglycidyl ether of biphenols such as p, p'-biphenol, etc.) ; novolac-type epoxy resins (for example, phenol novolak-type epoxy resins, cresol novolac-type epoxy resins, etc.); polyglycidyl ethers of polyhydroxyarene [eg, bis(glycidyloxy)benzene, bis(glycidyloxy)naphthalene, etc.]; tetrakis phenol-type epoxy compounds [eg, tetrakis (glycidyloxyphenyl) ethane, etc.]; polyglycidyl ethers of C _2-4 alkylene oxide adducts of aromatic polyols corresponding to these compounds; The compound etc. which made the glycidyl group in these compounds a 2-methyl glycidyl group are mentioned.

Examples of the alicyclic glycidyl ether type epoxy compound include polyglycidyl ethers of alicyclic polyols or alkylene oxide adducts thereof. For example, hydrogenated products of the aromatic glycidyl ether compounds [for example, , hydrogenated ratio or bisphenol type epoxy compound (diglycidyl ether of hydrogenated product of common bisphenols such as hydrogenated bisphenol A type epoxy compound); hydrogenated novolac-type epoxy resin, etc.]; bis(glycidyloxy) _C5-10 cycloalkanes such as 1,4-bis(glycidyloxy)cyclohexane; bis(glycidyloxy C _1-4 alkyl) C _5-10 cycloalkanes such as diglycidyl ether of 1,4-cyclohexanedimethanol; polyglycidyl ethers of C _2-4 alkylene oxide adducts of alicyclic polyols corresponding to these compounds; The compound etc. which made the glycidyl group in these compounds a 2-methyl glycidyl group are mentioned.

These glycidyl ether type epoxy compounds can also be used individually or in combination of 2 or more types. Among these, an aliphatic glycidyl ether type epoxy compound is preferable because it has a low viscosity and is easy to promote aggregation of the dielectric filler.

As an aliphatic glycidyl ether type epoxy compound, polyglycidyl ether of an aliphatic polyhydric alcohol (aliphatic polyol) or its condensate (or a multimer), etc. are mentioned, for example. As an aliphatic polyhydric alcohol for forming an aliphatic glycidyl ether type epoxy compound, For example, an aliphatic diol [For example, ethylene glycol, propylene glycol, 1, 3- propanediol, 1,2-butanediol, 1, 4- linear or branched C _2-12 alkanediol such as butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 8-octanediol, and 1, 10-decanediol]; trivalent or higher aliphatic polyols [For example, polymethylol alkane such as trimethylolpropane; sugar alcohols such as glycerin, pentaerythritol, sorbitol and mannitol; These alkylene oxide adducts, etc.] etc. are mentioned. In addition, the condensate of an aliphatic polyhydric alcohol may be a compound which these aliphatic polyhydric alcohols were condensed individually or in combination of 2 or more types.

Typical examples of the aliphatic glycidyl ether type epoxy compound include a divalent glycidyl ether type compound and a trivalent or higher glycidyl ether type compound. As a divalent glycidyl ether type compound, For example, (poly)alkylene glycol diglycidyl ether represented by following formula (1); and diglycidyl ether of the above trivalent or higher aliphatic polyols such as trimethylolpropane diglycidyl ether, glycerin diglycidyl ether, and pentaerythritol diglycidyl ether, or a condensate containing the polyol. .

[Tue 1]

(Wherein, A ¹ is a linear or branched alkylene group, m is an integer of 1 or more, and R ¹ each independently represents a hydrogen atom or a methyl group).

Examples of the linear or branched alkylene group represented by A ¹ in the formula (1) include an ethylene group, a propylene group, a trimethylene group, a 1,2-butanediyl group, a tetramethylene group, and 2,2- Linear or branched C _2-12 alkylene groups such as dimethylpropane-1, 3-diyl group (neopentylene group), pentamethylene group, hexamethylene group, octamethylene group, and decamethylene group (for example, straight-chain or a branched C _2-10 alkylene group), preferably a linear or branched C _2-8 alkylene group (eg, a straight or branched C _3-7 alkylene group), even more preferably an ethylene group, A linear or branched C _2-7 alkylene group such as a propylene group, trimethylene group, tetramethylene group, or hexamethylene group (For example, a linear or branched C _2-6 alkylene group such as a tetramethylene group, preferably preferably a linear or branched C _3-6 alkylene group, particularly a linear or branched C _4-6 alkylene group).

The number of repetitions m may be an integer of 1 or more, for example, may be selected from integers of about 1 to 30 (eg, 1 to 15), for example, 1 to 10 (eg, 1 to 8), preferably may be 1 to 6 (eg 1 to 4), even more preferably 1 to 3 (eg 1 or 2), in particular 1. If m is too large, the viscosity of the liquid precursor may increase and the controllability of the dielectric filler may decrease. In addition, when m is 2 or more, the kind of several alkylene group A ¹ may mutually be the same or different.

R ¹ may be either a hydrogen atom or a methyl group, and is usually a hydrogen atom in many cases. Although the types of R ¹ may be different from each other, they are usually the same.

Specifically, as the (poly)alkylene glycol diglycidyl ether represented by the formula (1), for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,3-propanediol di glycidyl ether, 1,2-butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1, Linear or branched C _2-12 alkylene glycol-diglycidyl ether, such as 6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, and 1, 10-decanediol diglycidyl ether cydyl ether; (di to penta) linear or branched C _2-12 alkylene glycol-diglycidyl such as diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, etc. ether; The compound etc. which substituted the glycidyloxy group of these compounds with the 2-methyl glycidyloxy group are mentioned.

The (poly)alkylene glycol diglycidyl ether represented by the formula (1) may be used alone or in combination of two or more. Among these, alkylene glycol diglycidyl ether in which m is 1 is preferable, and among them, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neo linear or branched C _2-8 alkylene glycol-diglycidyl ethers such as pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether (for example, linear or branched C _3-7 alkylene glycol-diglycidyl ethers), in particular straight or branched C _2-6 alkylene glycol-diglycidyl ethers (eg neopentyl glycol, 1,6-hexanediol diglycidyl linear or branched C _4-6 alkylene glycol-diglycidyl ether such as cidyl ether, preferably branched C _4-6 alkylene glycol-diglycidyl ether such as neopentyl glycol) desirable.

On the other hand, as a trivalent or higher glycidyl ether compound, for example, (poly)trimethylolpropane tri to pentaglycidyl ether [for example, trimethylolpropane triglycidyl ether, ditrimethylolpropane triglycidyl ether , mono to tri(trimethylolpropane) tri to pentaglycidyl ether such as ditrimethylolpropane tetraglycidyl ether]; (poly)glycerin polyglycidyl ether [For example, mono-tri-(glycerin) tri-pentaglycidyl ether, such as glycerin triglycidyl ether, diglycerin triglycidyl ether, diglycerin tetraglycidyl ether, etc. ]; (poly) pentaerythritol polyglycidyl ether [eg, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether Mono-tri-(pentaerythritol) tri-octaglycidyl ether, etc.], such as dil ether, polyol of trivalence or more, or polyglycidyl of its condensate (or C _2-4 alkylene oxide adduct thereof) ether; The compound etc. which made the glycidyl group in these compounds a 2-methyl glycidyl group are mentioned.

These aliphatic glycidyl ether type epoxy compounds can also be used individually or in combination of 2 or more types. Among these aliphatic glycidyl ether-type epoxy compounds, divalent glycidyl ether-type compounds, especially, the polyvalent glycidyl ether-type compounds represented by the formula (1) ) Alkylene glycol diglycidyl ethers (especially alkylene glycol diglycidyl ethers) are well used.

The polyfunctional alicyclic epoxy compound may be a compound having two or more epoxy-containing groups and at least one of which is an alicyclic epoxy group. Typically, a compound having one alicyclic epoxy group and one or more non-alicyclic epoxy groups [for example, 1, 2:8, 9-diepoxy limonene (or 1-methyl-4-(2-methyloxiranyl)- 7-oxabicyclo[4.1.0]heptane, a compound each having one alicyclic epoxy group and one ethylene oxide group, such as "LIMONENE DIOXIDE" manufactured by ARKEMA); a compound having two alicyclic epoxy groups; The compound etc. which have 3 or more alicyclic epoxy groups are mentioned.

As a compound which has two alicyclic epoxy groups, the compound represented by following formula (2) is mentioned.

[Tue 2]

(Wherein, X represents a single bond or a linking group, and the cyclohexene oxide group may each have a substituent).

In Formula (2), as a linking group represented by X, for example, a divalent hydrocarbon group, an alkenylene group in which some or all of carbon-carbon double bonds are epoxidized, a carbonyl group (-CO-), an ether bond (- O-), an ester bond (-COO-), a carbonate group (-O-CO-O-), an amide group (-CONH-), and a group in which a plurality of these groups are linked.

Examples of the divalent hydrocarbon group include a linear or branched C _1-18 alkylene group and a divalent C _3-18 alicyclic hydrocarbon group. Examples of the linear or branched C _1-18 alkylene group include a methylene group, a methyl methylene group, a dimethyl methylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent C _3-18 alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, and 1,3-cyclo Cycloalkylene groups (including a cycloalkylidene group), such as a hexylene group, a 1, 4- cyclohexylene group, and a cyclohexylidene group, etc. are mentioned.

Examples of the alkenylene group in the alkenylene group in which some or all of the carbon-carbon double bonds are epoxidized (also referred to as "epoxidized alkenylene group") include, for example, a vinylene group, a propenylene group, 1- and linear or branched C _2-8 alkenylene groups such as butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, and octenylene group. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all carbon-carbon double bonds are epoxidized, and more preferably a C _2-4 alkenylene group in which all carbon-carbon double bonds are epoxidized. .

Among these, as X, a carbonyloxymethylene group etc. are preferable.

In the formula (2), two cyclohexene oxide groups may each independently have a substituent bonded thereto, and examples of the substituent include a halogen atom, a C _1-10 alkyl group, a C _1-10 alkoxy group, and C _{2 -10} alkenyloxy group, C _6-14 aryloxy group, C _7-18 aralkyloxy group, C _1-10 acyloxy group, C _1-10 alkoxycarbonyl group, C _6-14 aryloxycarbonyl group, C _{7 -18} aralkyloxycarbonyl group, epoxy group-containing group, oxetane ring-containing group, C _1-10 acyl group, isocyanate group, sulfo group, carbamoyl group, oxo group and the like. It is preferable that the said substituent is not couple|bonded with the cyclohexene oxide group.

Representative examples of the compound represented by the formula (2) include (3, 4, 3', 4'-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy- 1,2-Bis(3,4-epoxycyclohexan-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexan-1-yl)propane, 1,2-bis(3,4- Epoxycyclohexan-1-yl) ethane, the compound represented by following formula (2-1) - (2-8), etc. are mentioned.

[Tuesday 3]

(Wherein, L represents a C _1-8 alkylene group (for example, a linear or branched C _1-3 alkylene group such as a methylene group, ethylene group, propylene group, isopropylene group), and n1 and n2 are Each represents an integer from 1 to 30).

As a compound which has the said 3 or more alicyclic epoxy group, the compound etc. which are represented by following formula (2-9) and (2-10) are mentioned, for example.

[Tue 4]

(In the formula, n3 to n8 each independently represent an integer of 1 to 30).

These polyfunctional alicyclic epoxy compounds may be used individually or in combination of 2 or more types. Among these polyfunctional alicyclic epoxy compounds, compounds having two alicyclic epoxy groups, such as the compound represented by the formula (2), are preferable, and among these, 3,4-epoxycyclohexylmethyl in which X is a carbonyloxymethylene group. (3,4-epoxy) cyclohexane carboxylate (compound represented by the said Formula (2-1)) is preferable.

As another polyfunctional epoxy compound different from the said polyfunctional glycidyl type epoxy compound and polyfunctional alicyclic epoxy compound, 1,2-epoxy-4- (2-oxiranyl) of a polyol (trimethylol propane etc.), for example. A cyclohexane adduct (For example, Daicel Corporation "EHPE3150" etc.) etc. are mentioned.

These polyfunctional epoxy compounds may be used individually or in combination of 2 or more types. Among these epoxy compounds, a polyfunctional epoxy compound is usually used well from a viewpoint of sclerosis|hardenability and productivity. Among polyfunctional epoxy compounds, polyfunctional glycidyl-type epoxy compounds and polyfunctional alicyclic epoxy compounds are preferable from the viewpoints of curability and productivity particularly suitable for aggregation of dielectric fillers, and even more preferably, glycidyl ether-type epoxy compounds. , a compound having two alicyclic epoxy groups, more preferably a (poly)alkylene glycol diglycidyl ether represented by the formula (1), a compound having two alicyclic epoxy groups represented by the formula (2) to be.

In addition, the combination of a polyfunctional alicyclic epoxy compound and a polyfunctional glycidyl-type epoxy compound is preferable from the viewpoint that the controllability of the dielectric filler is excellent and the flexibility of the molded article can be improved. A combination of a compound having two alicyclic epoxy groups and a (poly)alkylene glycol diglycidyl ether represented by the formula (1) is particularly preferred.

The mass ratio of the polyfunctional alicyclic epoxy compound and the polyfunctional glycidyl type epoxy compound can be selected from the range of the former/the latter = 99/1 to 1/99, for example, 90/10 to 10/90, preferably 80 /20-20/80, More preferably 70/30-30/70, More preferably, it is 60/40-40/60.

Since the aggregation of the dielectric filler in the aggregation step can be promoted, the viscosity of the cationically polymerizable compound at 25°C is, for example, in the range of about 500 mPa·s or less (eg, 1-400 mPa·s). can be selected from, for example, 2 to 350 mPa·s (eg, 3 to 300 mPa·s), preferably 4 to 250 mPa·s (eg, 5 to 200 mPa·s), more preferably is 5 to 150 mPa·s (eg 5 to 100 mPa·s), still more preferably 5 to 80 mPa·s (eg 5.5 to 50 mPa·s), and among these, preferably 6 to 30 mPa·s (eg, 6.5 to 20 mPa·s), even more preferably about 7 to 15 mPa·s (eg, 7.5 to 10 mPa·s). In addition, the viscosity can be measured using a conventional viscometer (eg, a single cylindrical rotational viscometer, etc.).

The ratio of the cationically polymerizable compound can be selected from the range of, for example, about 10 to 100% by mass (eg, 30 to 99% by mass) with respect to the entire resin contained in the liquid precursor, for example, 50 to 100% by mass % (for example 60-98 mass %), Preferably 70-100 mass % (for example 80-97 mass %), More preferably, 80-100 mass % (for example 90-95 mass %) , in particular, may be about 95 to 100 mass % (especially, substantially 100 mass %). When there are too few ratios of a cationically polymerizable compound, there exists a possibility that an aggregation part cannot be formed simply or sufficiently (or precisely) in an aggregation process.

As curable resin, a photocurable resin is preferable at the point which it is easy to form an aggregation part, and a photocationically polymerizable compound is especially preferable.

(Polymerization Initiator)

The molded article (or the liquid precursor for forming the molded article) may further contain a polymerization initiator for polymerizing the resin. The polymerization initiator can be appropriately selected according to the type of resin, and when the resin is a curable resin, a radical polymerization initiator, a cationic polymerization initiator, or an anionic polymerization initiator may be used. A preferred polymerization initiator is a cationic polymerization initiator (acid generator). Cationic polymerization initiators include photo acid generators and thermal acid generators.

Examples of the photoacid generator include sulfonium salts (salts of sulfonium ions and anions), diazonium salts (salts of diazonium ions and anions), iodonium salts (salts of iodonium ions and anions), selenium salts. (salt of selenium ion and anion), ammonium salt (salt of ammonium ion and anion), phosphonium salt (salt of phosphonium ion and anion), oxonium salt (salt of oxonium ion and anion), transition metal complex ion and anion salts, bromine compounds, and the like. These photoacid generators can be used individually or in combination of 2 or more types. Among these photoacid generators, an acid generator with high acidity, for example, a sulfonium salt, is preferable from the viewpoint of improving the reactivity.

Examples of the sulfonium salt include triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris(4-methoxyphenyl)sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naph Tyldiphenylsulfonium salt, tris(4-fluorophenyl)sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris(4-hydroxyphenyl)sulfonium salt, diphenyl[4- (phenylthio)phenyl]sulfonium salt, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium salt, 4-(p-tolylthio)phenyldi-(p-phenyl)sulfonium salt, etc. triarylsulfonium salts; diarylsulfonium salts such as diphenylphenacylsulfonium salt, diphenyl 4-nitrophenacylsulfonium salt, diphenylbenzylsulfonium salt, and diphenylmethylsulfonium salt; monoarylsulfonium salts such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, and 4-methoxyphenylmethylbenzylsulfonium salt; and trialkylsulfonium salts such as dimethylphenacylsulfonium salt, phenacyltetrahydrothiophenium salt and dimethylbenzylsulfonium salt. These sulfonium salts can be used individually or in combination of 2 or more types. Among these sulfonium salts, a triarylsulfonium salt is preferable.

As an anion (counter ion) for forming a salt with a cation, for example, SbF ⁶ - , PF ⁶ - , BF ⁴ - , fluorinated alkylfluorophosphate ion [(CF ₃ CF ₂ ) ₃ PF ³ - , (CF ₃ ) CF ₂ CF ₂ ) ₃ PF ^3- etc], (C ₆ F ₅ ) ₄ B-, (C ₆ F ₅ ) ₄ Ga ^- , sulfonic acid anion (trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, nona Fluorobutanesulfonic acid anion, methanesulfonic acid anion, benzenesulfonic acid anion, p-toluenesulfonic acid anion, etc.), (CF ₃ SO ₂ ) ₃ C ^- , (CF ₃ SO ₂ ) ₂ N ^- , perhalogenate ion, halogenated sulfonic acid ion , sulfate ion, carbonate ion, aluminate ion, hexafluorobismuth acid ion, carboxylate ion, aryl borate ion, thiocyanate ion, nitrate ion, etc. are mentioned. These anions may be used individually or in combination of 2 or more types. Among these anions, SbF ⁶ - , PF ⁶ - , fluorinated alkyl fluorophosphate ion, etc. are commonly used. From the viewpoint of solubility, fluorinated alkyl fluorophosphate ion and the like are preferred, and usually PF ⁶ - or the like is often used.

As the photo acid generator, a commercially available photo acid generator can be used. As a commercially available photoacid generator, "CPI-101A", "CPI-110A", "CPI-100P", "CPI-110P", "CPI" by San-Apro Ltd. are, for example, -210S", "CPI-200K"; "CYRACURE UVI-6990", "CYRACURE UVI-6992" manufactured by The Dow Chemical Company; "UVACURE1590" manufactured by DAICEL-ALLNEX LTD.; "CD-1010", "CD-1011", and "CD-1012" manufactured by Sartomer, USA; "Irgacure 264" manufactured by BASF; "CIT-1682" manufactured by Nippon Soda Co., Ltd.; Rhodia Japan Ltd. "PHOTOINITIATOR 2074", etc. can be used.

Examples of the thermal acid generator include arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes, and the like. These thermal acid generators can be used individually or in combination of 2 or more types. Among these thermal acid generators, an acid generator with high acidity, for example, an arylsulfonium salt, is preferable from the viewpoint of improving the reactivity. Examples of the anion include the same anion as that of the photoacid generator, and may be an antimony fluoride ion such as SbF ^6- .

As for the thermal acid generator, a commercially available thermal acid generator can be used. As a commercially available thermal acid generator, for example, "SAN-AID SI-60L", "San-Aid SI-60S" manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD., "San-Aid SI-80L", "San-Aid SI-100L", "SP-66", "SP-77" manufactured by ADEKA Corporation, etc. can be used.

In addition, these light or thermal acid generators may generate an acid by either action of light and heat, respectively.

These cationic polymerization initiators may be used individually or in combination of 2 or more types. Among these cationic polymerization initiators, a photoacid generator is preferable at the point which can form an aggregation part in pattern shape easily using a photomask etc.

The ratio of the polymerization initiator (particularly, cationic polymerization initiator) may be appropriately selected according to the type of resin, etc., and the curability of the liquid precursor may be adjusted, for example, 0.01 to 100 parts by mass of the total amount of the resin (especially the cationically polymerizable compound). It can select from the range of about -100 mass parts, For example, 0.1-50 mass parts, Preferably 1-30 mass parts, More preferably, 3-20 mass parts, More preferably, 5-15 mass parts, Most preferably, it is 8-12 mass parts. If the ratio of the polymerization initiator is too small, the curing reaction may hardly proceed and the dielectric filler may be difficult to aggregate in the agglomeration process. While there is a possibility of hardening, it also costs and it is disadvantageous also in the point of productivity.

(dielectric filler)

As the dielectric filler, a conventional dielectric filler (dielectric particle or granular dielectric) can be used. Common dielectric fillers can be roughly divided into inorganic fillers (or particles) and organic fillers (or particles).

The material of the inorganic filler includes a metal oxide, a metal composite oxide, and the like. Examples of the metal oxide include titanium oxide, zirconium oxide, and lanthanum oxide. Examples of the composite metal oxide include titanium metals such as magnesium titanate, calcium titanate, strontium titanate, barium titanate (BaTiO ₃ ), zinc titanate, and bismuth titanate; zirconate metals such as barium zirconate; stannate metals such as barium stannate; hafniate metals such as barium hafniate; metal niobates such as lithium niobate; tantalate metals such as lithium tantalate; and metal zirconate titanates such as barium titanate zirconate and lead zirconate titanate (PZT). The composite metal oxide such as barium titanate may further contain alkaline earth metals such as calcium and strontium, and rare earth metals such as yttrium, neodymium, samarium and dysprosium as trace components.

As the material of the organic filler, for example, polyvinylidene fluoride, vinylidene fluoride-ethylene trifluoride copolymer, vinylidene fluoride-ethylene tetrafluoride copolymer, vinylidene fluoride-vinylidene hexafluoride copolymer, etc. polymer; odd polyamides (odd nylon) such as polyamide 5, polyamide 7, and polyamide 11; cyano resins such as cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, cyanoethyl hydroxyethyl cellulose and cyanoethyl cellulose; polyurea; polythiourea; Triglycine sulfate, etc. are mentioned.

The dielectric filler formed of these materials can be used individually or in combination of 2 or more types. Among these, inorganic fillers are preferable from the viewpoint of easy formation of aggregates, and inorganic fillers (composite metal oxide fillers) formed of a composite metal oxide are still more preferable, and inorganic fillers formed of titanium-containing composite metal oxides are more preferable, and titanic acid An inorganic filler formed of an alkaline earth metal is most preferred. Further, the dielectric filler may be an inorganic filler having a perovskite structure (in particular, an inorganic filler formed of a composite metal oxide having a perovskite structure) in view of the ease of forming agglomerated portions. Further, among the dielectric fillers, the ferroelectric filler may be used in that the dielectric constant of the molded article can be improved.

The dielectric constant (ε _r ) of the dielectric filler may be 100 or more, for example, 500 or more, preferably 1000 or more, even more preferably 3000 or more (eg, 3000 to 10000).

The shape (shape of primary particles) of the dielectric filler is not particularly limited as long as it is granular, and examples thereof include spherical shapes such as true spherical shape or substantially spherical shape; ellipsoid (ellipsoid) phase; abstractions such as cones and polygons; polygonal cube shapes, such as a cube shape and a cuboid shape; Plate shape, such as a flat shape, a flaky shape, and a flaky shape; rod or rod; Line shape, such as fibrous shape and water needle shape; irregular shape, etc. are mentioned.

The central particle diameter (D ₅₀ ) of the dielectric filler may be 1 μm or more, but preferably 1 μm or less, and even more preferably 0.01 to 1 μm. If the central particle size is too small, the viscosity of the liquid precursor tends to rise, and there is a fear that the dielectric filler may be difficult to aggregate in the agglomeration step, or there is a risk that it may be difficult to effectively impart dielectric properties due to the influence of the interfacial resistance (contact resistance). Conversely, if it is too large, the dielectric filler may be difficult to move in the aggregation process, making it difficult to agglomerate. In addition, in order to efficiently increase the dielectric filler concentration of the agglomerated portion, particles of different sizes may be intentionally mixed in a predetermined ratio.

In addition, in the present specification and claims, the central particle diameter of the dielectric filler means the central particle diameter of primary particles, and a nanoparticle diameter distribution measuring device (“SALD-7500nano” manufactured by SHIMADZU CORPORATION) ) can be used to measure on a volume basis. In addition, it is calculated|required by the image analysis method. That is, an electron microscope image is taken for a sufficient number (for example, 10 or more) of particulate matter using, for example, a scanning electron microscope (SEM), and the maximum diameter, crossover diameter, and thickness of these particulate matter are measured. and it is obtained by arithmetic mean.

The ratio of the dielectric filler can be selected from the range of about 0.01 to 300 parts by mass (for example, 0.1 to 100 parts by mass) with respect to 100 parts by mass of the resin (or resin precursor), for example, 0.1 to 80 parts by mass, preferably is 0.2 to 70 parts by mass. Aggregation of the derivative filler can be controlled even if the proportion of the derivative filler is large, and the proportion of the derivative filler is, for example, from 1 to 300 parts by mass, preferably from 10 to 200 parts by mass, even more preferably from 100 parts by mass of the resin. 20-100 mass parts, More preferably, 30-80 mass parts may be sufficient. If the ratio of the dielectric filler is too small, there is a fear that the dielectric constant of the molded article cannot be improved, but in the present disclosure, even with a relatively small amount of the dielectric filler, the dielectric constant can be improved by forming the agglomerated portion. Conversely, if the amount is too large, the viscosity of the liquid precursor tends to increase, making it difficult for the dielectric filler to agglomerate in the agglomeration process. Furthermore, the softness|flexibility (or toughness) of the molded object obtained may fall easily, and there exists a possibility of becoming a soft molded object.

(other ingredients)

The molded article (or liquid precursor for forming the molded article) may further contain other components such as conventional additives, if necessary, in addition to the resin and dielectric filler.

Common additives include, for example, stabilizers (thermal stabilizers, ultraviolet absorbers, light stabilizers, antioxidants, etc.), dispersants, antistatic agents, colorants, lubricants, sensitizers (acridines, benzoflavins, perylenes, anthracenes, thioxanthone, laser dyes, etc.), sensitizers, curing accelerators (imidazoles, alkali metal or alkaline earth metal alkoxides, phosphines, amide compounds, Lewis acid complex compounds, sulfur compounds, boron compounds, condensable organometals) compound, etc.), an antifoaming agent, a flame retardant, and the like. These additives can be used individually or in combination of 2 or more types. The proportion of the usual additive is, for example, 30 parts by mass or less (for example, 0.01 to 30 parts by mass), preferably 20 parts by mass or less, still more preferably 10 parts by mass with respect to 100 parts by mass of the resin (or resin precursor). It may be less than

(characteristics of molded body)

As described above, the aggregation portion of the molded body is a region formed by aggregation of the dielectric filler without uniformly dispersing it inside the molded body by application of active energy. It has a structure in which the abundance ratio gradually decreases toward the interface. That is, the agglomerated portion does not have a homogeneous structure in which the dielectric filler is present in a constant ratio in the entire area of the agglomerated portion, but gradually (linearly or curvedly, or continuously or stepwisely) in concentration near the interface at least between the aggregated portion and the non-agglomerated portion. ) has a decreasing concentration gradient or gradient structure. In particular, since the structure in the vicinity of the interface has a concentration gradient but is not formal, it is impossible or extremely difficult to specify the microscopic structure, and is not practical. Moreover, by having this structural characteristic, the characteristic derived from this indication, such as an interface strength improvement by an anchor effect, can be provided. Such a structure can be easily observed with a digital microscope (CCD observation image). It can be easily confirmed that the abundance ratio (concentration) of the dielectric filler is non-uniform.

Incidentally, the non-uniformity of the abundance ratio (concentration) of the dielectric filler in the agglomerated portion is determined by elemental analysis (or surface analysis) or chemical species analysis of a predetermined region in the agglomerated portion to determine the elements constituting the dielectric filler (also referred to as dielectric filler constituent elements). ) or by detecting chemical species. The elemental analysis method (or apparatus) may be appropriately selected depending on the shape of the molded body (type of dielectric filler, etc.), for example, energy dispersive X-ray spectroscopy (EDX or EDS), wavelength dispersive X-ray spectroscopy (WDX) , WDS or EPMA), X-ray photoelectron spectroscopy (XPS or ESCA), Auger electron spectroscopy (AES), secondary ion mass spectrometry (SIMS) [time-of-flight secondary ion mass spectrometry (TOF-SIMS), etc.] Methods are mentioned, As a method of detecting a chemical species, common methods, such as Raman spectroscopy and infrared spectroscopy (IR), are mentioned, Usually, energy dispersive X-ray spectroscopy, such as SEM-EDX (SEM-EDS), is well used

In the molded article of the present disclosure, the dielectric filler concentration decreases or gradually decreases toward the interface (or the interface direction) in the peripheral region at least near the interface of the agglomerated portion. It can be confirmed that the abundance ratio of dielectric filler constituent elements in (or in the peripheral region) is low.

As a representative confirmation method, for example, first, the central portion of the agglomerated portion (the portion of the interior of the aggregated portion that is furthest from the interface with the non-agglomerated portion that adjacently divides the aggregated portion) and the interface between the aggregated portion and the adjacent non-agglomerated portion in the thickness direction In the cross section (or surface) of the molded body traversing along , the agglomerated portion is divided into three equal parts from the center toward the interface (or in the interface direction) (the distance from the center to the interface is equally spaced). Each divided region is divided in the order from the central portion toward the interface: a central region (central portion, near central region, or first region), intermediate region (middle region, intermediate region, or second region), and peripheral region (peripheral region, near interface or first region) 3 area). By elemental analysis of each of these regions, measuring the abundance ratio of at least one element constituting the dielectric filler, and comparing the abundance ratio of each region, the abundance ratio in the peripheral region is at least higher than the abundance ratio in the intermediate region. low can be seen. In addition, the abundance ratio may be a ratio based on the number of atoms (frequency or intensity), but is usually a ratio based on the mass of atoms. In the present specification and claims, specific elemental analysis methods include SEM-EDS ("SU5000" manufactured by Hitachi High-Technologies Corporation; SDD detector "X-X-EDS" manufactured by Oxford Instruments) MaxN”) can be used.

Hereinafter, it will be described in more detail based on FIG. 2 . Fig. 2 is a schematic partial longitudinal sectional view of a molded article of the present disclosure, that is, a film (or sheet)-like molded article having agglomerated portions 1 in the form of dielectric fillers penetrated in the thickness direction. That is, Fig. 2 shows a central axis 4 (a central axis extending from the center in the planar direction of the agglomerated portion in the thickness direction) of any agglomerated portion 1 in the molded article, and a non-agglomerated portion adjacent to the aggregated portion 1 ( While passing (or crossing) the interface 3 with 2), the cross-section (or longitudinal cross-section) substantially parallel to the thickness direction of the molded object is shown.

In the figure, within the aggregation part, the area from the central part 4 to at least one interface (the left interface of the central part 4 in the figure) 3 is defined as the area from the central part 4 to the interface. The distance to (3) is divided into three in the width direction (lateral direction) of the agglomeration part so that the distance to (3) is equal. The divided regions are defined as the central region 1a, the intermediate region 1b, and the peripheral region (or near the interface) 1c in the order from the region on the central portion 4 side toward the interface 3 . In each of the regions 1a to 1c, elemental analysis is performed at a plurality of randomly selected (preferably 3 or more) measurement points, and the abundance ratio of at least one element among the dielectric filler constituent elements is determined for each measurement location. An average value of the obtained abundance ratio is calculated, and is employed as the abundance ratio of each region to which the measurement location belongs. By comparing the abundance ratio of the dielectric filler constituent elements in the respective regions obtained in this way, it can be confirmed that the abundance ratio (concentration) of the dielectric filler in the aggregation portion is non-uniform.

More specifically, the distribution state of the dielectric filler in the agglomerated portion of the cross section of the molded body (the longitudinal section passing through the center and the interface of the agglomerated portion) is determined by taking the abscissa in the transverse direction in the cross section of the molded body (the direction perpendicular to the thickness direction, or the agglomerated portion width direction) and the vertical axis representing the abundance ratio (dielectric filler concentration) of one element selected from dielectric filler constituent elements. In the molded article of the present disclosure, the abundance ratio (concentration) in the peripheral region is at least lower than the abundance ratio (concentration) in the intermediate region, perhaps because agglomerated portions are formed by the movement of the dielectric filler. For this reason, as the shape (concentration distribution of the agglomerated portion in the longitudinal section) shown in the graph (a graph in which the horizontal axis is a section from one peripheral region through the central region (or central region) to the other peripheral region), a mountain-shaped or Normal distribution [a shape in which the abundance ratio of the central area is high, and is linearly or curved toward the peripheral area (interfacial direction) and decreases continuously or stepwise]; trapezoidal shape [a shape in which the abundance ratio of the central area and the intermediate area is almost the same, and is linearly or curved toward the peripheral area and decreases continuously or stepwise]; a caldera phase [a shape in which the abundance ratio of the intermediate region is high, and is linear or curved toward the central region and the peripheral region, and decreases continuously or in stages], etc. are mentioned, and they are usually in the shape of a mountain. In addition, the graph shape (concentration distribution) may be satisfied for at least one of the dielectric filler constituent elements, preferably for a plurality of dielectric filler constituent elements, and even more preferably for all dielectric filler constituent elements. may be satisfied (the same applies to the ratio of abundance described below).

The ratio of the abundance ratio in the peripheral region (third region) to the abundance ratio in the intermediate region (second region) is, for example, 3rd region/second region (by mass) = 1/1.01 to 1/ It can be selected from the range of about 20 (eg, 1/1.05 to 1/15), for example, 1/1.1 to 1/10 (eg, 1/1.15 to 1/8), preferably 1/1.2 ~1/7 (eg 1/1.25-1/6), even more preferably 1/1.5-1/5 (eg 1/2-1/4, preferably 1/2.5-1/3.5) ) may be about.

In addition, the abundance ratio of the peripheral region (near the interface or the third region) may not necessarily be lower than the abundance ratio of the central region (the first region), but is usually low in many cases. Therefore, the ratio of the abundance ratio in the third region to the abundance ratio in the first region is, for example, 3rd region/first region (by mass) = 1/1.1 to 1/20 (eg 1 /1.2 to 1/15), preferably 1/1.3 to 1/10 (for example, 1/1.5 to 1/8), even more preferably 1/2 to 1/7 ( For example, it may be about 1/3 to 1/6, preferably 1/3.5 to 1/5.5). The ratio of the abundance ratio in the second region to the abundance ratio in the first region is, for example, second region/first region (by mass) = 1/0.1 to 1/5 (eg 1/0.5). It can be selected from the range of about 1/4), for example, 1/0.8 to 1/3 (for example, 1/1 to 1/2.5), preferably 1/1.1 to 1/2 (for example, It may be about 1/1.2 to 1/1.8).

In addition, when measured by SEM-EDX, the abundance ratio may be the abundance ratio of one element selected from the dielectric filler constituent elements, and the total abundance ratio of all elements constituting the dielectric filler and carbon constituting the resin. It may be a ratio of the abundance ratio of one element selected from dielectric filler constituent elements. In addition, the preparation method of the analyte sample to be used for elemental analysis is not particularly limited as long as it does not affect the measurement result of the abundance ratio, and a conventional method, for example, a molded article is cut and the cross-section (or observation surface) is obtained. After being cut out, it may be prepared by, for example, a method of embedding in a predetermined resin and precision polishing, or an element not contained in the resin and dielectric filler may be vapor-deposited on the observation surface according to an analysis method or the like.

In addition, in the above description, although the method for confirming the non-uniformity of the abundance ratio (concentration) of the dielectric filler by elemental analysis has been described, instead of elemental analysis, the filler concentration such as a method of analyzing the chemical species is detected (or confirmed) ) can be used as well.

In addition, although the region in the cross section has been described in FIG. 2 , if the dielectric filler is a molded body having agglomerates in the form of penetrating or exposed surfaces, instead of the cross section, the region is set in the same manner on the surface of the molded body, and dielectric filler constituent elements It is also possible to compare the abundance of In general, in many cases, the area is set in the cross section, and the cross section may be any cross section, but a cross section (longitudinal cross section) substantially parallel to the thickness direction is preferable.

The central portion of the agglomerated portion can be appropriately determined according to the shape of the agglomerated portion. Due to the relationship with the manufacturing method (aggregation step) described later, the agglomerated portion is usually formed extending in the thickness direction or in a direction forming a predetermined angle to the thickness direction (preferably in the thickness direction). Therefore, the central portion passes through the center of the aggregated portion (or aggregated portion element) in the cross-section (cross-section perpendicular to the thickness direction) of the molded body [the center of the cross-sectional shape of the aggregated portion or the center in the width direction (if linear)] , may be a central axis (or a central plane) extending along a direction (or thickness direction) in which the agglomeration portion extends.

The cross-sectional shape of the aggregation part (or agglomeration part element) in the cross section is not particularly limited, and may be a shape corresponding to the shape of the agglomeration part to be described later, for example, a substantially circular shape, an approximately oval shape, or a polygonal shape (triangular shape, square shape, rectangular shape, etc.), linear shape (linear shape or curved shape), swirl shape, irregular shape, etc. are mentioned.

In the present specification and claims, when an agglomerate is formed of a plurality of agglomerate elements that are the same or different in shape and/or direction (eg, a complex (or irregular) shape (eg, a plurality of agglomerate elements) For example, in the case of forming agglomerated portions in a lattice shape), the central portion of the complex-shaped aggregated portion is a central portion of at least one aggregated portion element selected from the aggregated portion elements (the center of the cross-sectional shape of the aggregated portion element or (In the case of a linear) center in the width direction]. The aggregation element element has a relatively simple cross-sectional shape (for example, the cross-sectional shape of the above example) in many cases, and as a specific shape of the aggregation element element, for example, a dot shape [cylindrical shape, a square column shape (or rectangular prism), etc.], linear (a wall shape extending linearly or curvedly), etc. may be sufficient.

Representative examples of the complex-shaped aggregated portion include, for example, a U-shaped aggregate portion in a cross-section (for example, a pair of rectangular parallelepiped elements (or linear elements of a predetermined length) opposed to each other and connected to one end thereof, respectively. and an aggregation portion formed of the rectangular parallelepiped elements extending in opposite directions of the pair of rectangular parallelepiped elements, etc.]; a cross-section dumbbell-shaped agglomeration portion (eg, an aggregation portion formed of a rectangular parallelepiped element and a pair of cylindrical elements connected to both ends of the element, etc.); frame-like aggregation portions (eg, aggregation portions in which a predetermined region such as triangular frame-shaped aggregated portions and rectangular frame-shaped aggregated portions is partitioned by wall-shaped aggregated portion elements, etc.); A lattice-like aggregation portion (for example, a plurality of first linear elements extending parallel to each other at a predetermined distance and intersecting the plurality of first linear elements at a predetermined angle and parallel to each other at a predetermined interval It may be an aggregation part formed of a plurality of second linear elements extending; a honeycomb shape or a mesh-like aggregation part, etc.).

Since the dielectric filler is aggregated in the aggregated portion, the aggregated portion in the molded body functions as a region in which the function of the dielectric filler is expressed. Therefore, the agglomerated portion in the molded body is formed in various shapes and structures depending on the use or purpose. In the present disclosure, even a complex shape and structure can be easily formed by a simple method of applying active energy to a partial region.

It does not specifically limit as a shape of an aggregation part, For example, linear shape, column shape (or rod shape), spherical shape, ellipsoid shape, an irregular shape, planar shape, etc. are mentioned. In addition, the shape of the agglomeration part may be a shape that combines the above shapes (eg, a lattice shape, etc.) or a shape corresponding to the above cross-sectional shape. Among these shapes, a linear shape, a columnar shape (a columnar shape, a prismatic shape, etc.), a planar shape, a lattice shape, or a shape combining these shapes is well used.

The shape of the agglomeration portion can be selected from the above shapes, but it may be formed in a pattern (pattern or pattern shape) from the viewpoint of high productivity and improving the mechanical properties of the molded article by symmetry and homogeneity. The pattern shape may be formed by one aggregated portion (continuous single aggregated portion), and usually a plurality of aggregated portions separated from each other are often formed. The pattern may be, for example, a pattern (geometric shape, etc.), a pattern, a symbol (or mark), a character, a picture, a combination of two or more thereof, or the like, and designability can be imparted to the molded body by such a pattern shape. As a typical pattern, it may be a pattern on the plane of a film-shaped molded object normally, for example, regular or irregularly arranged dot shape, parallel or non-parallel at predetermined intervals (for example, equal intervals, mutually different intervals, etc.) and a straight or curved shape (line shape), a grid shape, a well-defined shape, a frame shape, a vortex shape, and combinations of two or more thereof. Examples of the shape (or the shape of a cross-section perpendicular to the thickness direction) of regularly or irregularly arranged dot-like aggregates include a polygonal shape such as a square shape, a circular shape, a star shape, an irregular shape, a combination of two or more thereof, and the like. .

The molded article of the present disclosure may have a single continuous agglomerated portion (eg, agglomerated portions forming a lattice pattern, etc.), or may have a plurality of agglomerated portions separated from each other. Among these, it is preferable to have a plurality of aggregated portions from the viewpoint of easily imparting anisotropy to the function of the aggregated portion and improving the mechanical properties of the molded article by reducing the ratio of the dielectric filler. When the molded article has a plurality of aggregated portions, the shape of each aggregated portion may be the same or different. In the present disclosure, by combining a mask of various shapes corresponding to the region to which active energy is applied (polymerization region or curing region) and a three-dimensional mold for molding a resin into a predetermined shape, it is possible to easily form agglomerate portions of various shapes. Also, a molded article having a different shape of each aggregation portion can be easily formed. From the viewpoint of productivity and the like, a molded article having substantially the same shape of the agglomerated portion is preferable. Among them, a plurality of aggregated portions form a pattern shape, and at least one aggregated portion of the plurality of aggregated portions extends in the thickness direction to cross (or penetrate) a film-like molded article (especially a dielectric film or sheet). may be In addition, the aggregation part (both ends in the thickness direction) may be exposed on the surface (particularly, both of the front surface and the back surface) of a sheet-like molded object.

In addition, the size (or the minimum width in the shape of the agglomerated part viewed in the thickness direction) such as the width or diameter of the agglomerated part is not particularly limited, and may be, for example, 1 mm or more, but in the present disclosure, a relatively small size (for example, 1 mm or less) can be formed. Therefore, the size of the aggregation portion may be selected from the range of about 0.01 to 500 μm (eg, 0.1 to 300 μm), for example, 1 to 200 μm or less, preferably about 10 to 150 μm.

The molded object of the present disclosure may have any shape of a one-dimensional shape (eg, fibrous), a two-dimensional shape (eg, plate-like, sheet-like, film-like, etc.), and three-dimensional molded body. Among these, a two-dimensional image is well used.

The thickness (average thickness) of the two-dimensional molded body can be selected from, for example, a range of about 0.1 µm to 1 mm, for example, 0.5 to 500 µm (eg, 1 to 100 µm), preferably 3 to 80 µm. μm (for example, 5-50 μm), even more preferably about 8 to 45 μm (for example, 10-40 μm). For example, 10 to 100 μm), preferably 20 μm or more (eg, 25 to 70 μm), even more preferably about 30 to 50 μm.

[Method for producing molded article]

The method for manufacturing a molded article of the present disclosure includes an aggregation process of aggregating the dielectric filler by applying active energy to a partial region of a liquid precursor including a resin precursor and a dielectric filler. In the aggregation step, when active energy is applied to a partial region, the resin precursor polymerizes, and the dielectric filler uniformly dispersed inside the molded body moves and aggregates in a partial region inside the liquid precursor. The partial region where the dielectric filler aggregates is either a region to which no active energy is applied (unpolymerized region or unexposed region) or a region to which active energy is applied (polymerized region or exposed region). In the method of the present disclosure, aggregation can be achieved in either of the unpolymerized region and the polymerized region by adjusting the combination of blending and manufacturing conditions (particularly, the type of resin and dielectric filler to be combined). Therefore, when the target aggregation form is determined, it is confirmed in advance whether the condition or combination for the dielectric filler to move to the non-polymerized region or the polymerized region by application of active energy, and then, when moving to the non-polymerized region, the target When the active energy is applied to a region other than the region corresponding to the aggregation form, and conversely, when moving to the polymerization region, the desired pattern can be formed simply by applying the active energy to the region corresponding to the desired aggregation form. .

In the present disclosure, although the detailed mechanism by which the dielectric filler exhibits this behavior is unclear, in the region to which the active energy is imparted, the resin precursor polymerizes to produce a resin, so that the resin component [resin precursor and its polymer (cured product)) It can be presumed that this is because there is a change in the affinity relationship between the resin] and the dielectric filler.

In the present disclosure, since the agglomerated portion is formed in this way, it is possible to suppress the occurrence of voids (voids generated at the resin/filler interface, etc.) frequently seen in the resin molded body containing the filler. Further, when the dielectric filler is aggregated in the polymerization region, the thickness of the aggregated portion may be greater than the thickness of the non-agglomerated portion.

In the aggregation process, the resin precursor can be selected according to the type of resin, and when the resin is a thermoplastic resin, it may contain a monomer (monofunctional polymerizable compound) for forming the thermoplastic resin as a polymerizable compound, and the resin In the case of a cured product of a curable resin (such as a cured product having a three-dimensional network structure), a polyfunctional polymerizable compound may be included.

The liquid precursor may not contain a solvent (or dispersion medium), and if necessary, in addition to the cationically polymerizable compound and filler (and other additives if necessary), a solvent is further included to reduce the viscosity of the liquid precursor, there may be

As the solvent (or dispersion medium), for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane etc.), alicyclic Formula hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (acetic acid esters such as methyl acetate, ethyl acetate, n-butyl acetate, etc.) ), water, alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves [methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether (1-methoxy-2-propanol), etc.], cello Solve acetates, sulfoxides (dimethyl sulfoxide, etc.), amides (dimethylformamide, dimethyl acetamide, etc.), carbonates [eg, chain carbonates such as dimethyl carbonate and diethyl carbonate, ethylene carbonate, propylene cyclic carbonates, such as carbonate (or propylene carbonate)], etc. can be illustrated. In addition, the solvent may be a mixed solvent. Among these solvents, alcohols, such as 2-propanol, carbonates, such as propylene carbonate, esters, such as n-butyl acetate, etc. are used well.

The viscosity of the solvent at 20°C is, for example, 0.5 to 100 mPa·s (eg, 0.6 to 50 mPa·s), preferably 0.5 to 20 mPa·s (eg, 0.7 to 10 mPa·s) , more preferably 0.5 to 5 mPa·s (eg, 1 to 3 mPa·s). In addition, the viscosity can be measured using a conventional viscometer (single cylindrical rotational viscometer, etc.). When the viscosity of the solvent is too high, there is a possibility that the viscosity of the liquid precursor cannot be sufficiently reduced.

When a solvent is included, the ratio is, for example, 300 mass parts or less (for example, 1-200 mass parts) with respect to 100 mass parts of liquid precursors, Preferably, 180 mass parts or less (for example, 50-150 mass parts) part), Preferably it is about 130 mass parts or less (for example, 80-120 mass parts). When there is too little quantity of a solvent, there exists a possibility that the viscosity of a liquid precursor may become unable to fully reduce, and when too large, there exists a possibility that it may become difficult to prepare a molded object with large thickness.

The liquid precursor for imparting active energy may be filled in a mold depending on the desired shape, or may be applied in the case of a sheet or film molded article. As the application method, a conventional method, for example, a roll coater, an air knife coater, a blade coater, a rod coater, a reverse coater, a bar coater, a comma coater, a dip squeeze coater, a die coater, a gravure coater, a micro gravure coater, a silk screen The coater method, the dip method, the spray method, the spinner method, etc. are mentioned.

Examples of the active energy include thermal energy by a laser or the like, and active rays such as ultraviolet rays or electron beams. Among these, actinic rays, such as an ultraviolet-ray and an electron beam, are preferable, and an ultraviolet-ray is especially preferable from points, such as handleability.

In the method of imparting active energy, an energy source (heat source or light source) may be selected according to the type of active energy. When the active energy is ultraviolet light, as a light source, for example, in the case of ultraviolet light, a deep UV lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a halogen lamp, a laser light source (a helium-cadmium laser, a light source such as an excimer laser) etc. can be used.

When ultraviolet light is used as actinic light (light energy), the illuminance may be appropriately selected depending on the type or concentration of the polymerizable compound, and the illuminance at a wavelength of 365 nm, for example, 0.1 to 20 mW/cm ² (for example, For example 1-18 mW/cm ² ), preferably 0.3-15 mW/cm ² (eg 5-12 mW/cm ² ), even more preferably 0.6-10 mW/cm ² (eg 6- 9.5 mW/cm ² ). The irradiation time may be selected according to the illuminance, for example, 1 to 60 minutes, preferably 3 to 25 minutes, still more preferably about 5 to 15 minutes.

In the aggregation step, by applying active energy to a partial region of the liquid precursor, polymerization of the resin precursor in the given region can be started, and at the same time, the dielectric filler moves to the part to which the active energy is not applied or to the part to which the aggregation part is formed. A non-agglomerated portion may be formed. In this step, polymerization of the resin precursor may be completed, or polymerization may be completed in a polymerization step to be described later.

As a method of imparting active energy to a partial region of the liquid precursor (or A-stage precursor), it can be appropriately selected depending on the type of activation energy, for example, in the case of thermal energy, laser light or the like may be irradiated to a partial region. , in the case of actinic rays such as ultraviolet rays or electron beams, by using a photomask having a region that can block the actinic rays in the uncured region (or unpolymerized region) may investigate.

In the case of forming a sheet-like molded body, active energy may be applied (or irradiated) in a direction inclined at a predetermined angle with respect to a flat liquid precursor such as a coating film in the agglomeration step, but in general, it is approximately perpendicular to the flat liquid precursor. It is preferable to irradiate in the phosphorus direction. By irradiating approximately vertically, the dielectric fillers are aggregated or oriented (regularly or randomly oriented) in the thickness direction of the sheet-like molded article to extend in the thickness direction (irradiation direction), and the dielectric fillers cross or penetrate ( Alternatively, it is possible to easily form agglomerates in the form in which the dielectric filler is exposed on the surface.

In the method for producing a molded body of the present disclosure, in addition to the aggregation step, the region (uncured region or It is preferable to further include a polymerization completion step of completing polymerization by imparting active energy to the unpolymerized region). By passing through the polymerization completion step, the resin precursor in the region to which no active energy is applied can also be polymerized to form a resin.

The region to which the activation energy is applied in the polymerization completion process may be any region including the region to which the activation energy is not applied in the aggregation process, but it can be easily manipulated, has excellent productivity, and the polymerization proceeds further to improve the mechanical properties of the molded body. From the viewpoint of improving the properties, a method in which active energy is applied to the entire area is preferred.

As the active energy, the same active energy as in the aggregation step may be used, and the conditions for applying the active energy may be usually changed in a direction to become stronger. In addition, it is also possible to irradiate by increasing the illuminance step by step. When using actinic light (light energy), there exists a possibility that productivity may fall when irradiation time is too long.

In addition, in the form in which the resin is a cationically polymerizable compound, by applying heat energy (or annealing treatment) in the polymerization completion step, polymerization can be completed using a dark reaction (post polymerization) of the cationically polymerizable compound. As annealing temperature, it is 50-200 degreeC (for example, 70-180 degreeC), for example, Preferably it is 80-150 degreeC (for example, 90-130 degreeC), More preferably, it may be about 100-120 degreeC. The heating time may be, for example, 10 to 120 minutes, preferably about 30 to 60 minutes.

In addition, in the present disclosure, a bonded body (composite molded body) in which the substrate and the molded body are joined may be formed by molding the molded body in a state in which the liquid precursor is brought into contact with a predetermined substrate by a method such as coating.

The material of the base material is not particularly limited, and either an organic material or an inorganic material may be used.

Examples of the organic material include resins [eg, olefin resins such as polyethylene and polypropylene, styrene resins such as ABS resins, vinyl resins such as vinyl chloride resin, (meth) such as polymethyl methacrylate) acrylic resins, polyester resins such as polyethylene terephthalate (PET), polycarbonate resins, polyamide resins, polyimide resins, cellulose derivatives such as cellulose esters and cellulose ethers, thermoplastic elastomers, etc.]; synthetic rubber materials (isoprene rubber, butyl rubber, etc.); foams of resins or rubbers (eg, polyurethane foam, polychloroprene rubber, etc.); Plant or animal-derived materials (wood, pulp, natural rubber, leather, wool, etc.) etc. are mentioned.

Examples of the inorganic material include ceramics (glass, silicon, cement, etc.); metals [for example, simple metals (aluminum, iron, nickel, copper, zinc, chromium, titanium, etc.), alloys containing these metals (aluminum alloy, steel (stainless steel, etc.), etc.), etc. are mentioned. .

Among these materials, resins (for example, polyester resins, polyimide resins, etc., preferably polyimide resins etc.), ceramics (glass etc.), and metals (copper etc.) are well used.

In addition, the form (shape) of a base material is not restrict|limited in particular, For example, one-dimensional shape, such as fibrous form (filament form, rope form, wire form, etc.), plate form, sheet form, film form, foil form , two-dimensional shapes such as cloth or cloth (woven fabric, knitted fabric, non-woven fabric, etc.), paper-like (fine paper, glassine paper, kraft paper, Japanese paper, etc.), Three-dimensional shapes, such as block shape, rod shape (cylindrical shape, polygonal pillar shape, etc.), and a tubular shape, etc. are mentioned.

Two-dimensional shapes, such as a plate shape, a sheet shape, a film shape, and foil shape, among these forms in many cases.

In addition, each aspect disclosed herein may be combined with any other feature disclosed herein.

Example

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited by these Examples. The raw material used was as follows, and the following method evaluated the obtained laminated body.

[Raw material]

(cationically polymerizable compound)

NPG: neopentyl glycol diglycidyl ether, Yokkaichi Chemical Co., Ltd. "EPOGOSEY (registered trademark) NPG(D)", viscosity 8 mPa·s ( 25℃, catalog value)

EP1: CEL2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate, Daicel Co., Ltd. "CELLOXIDE 2021P", viscosity 240 mPa·s (25°C)

EP2: (3, 4, 3', 4'-diepoxy)bicyclohexyl, viscosity 60 mPa s (25° C.)

(dielectric filler)

BaTiO ₃ : Barium titanate fine particles, Kanto Chemical Co., Ltd., particle size about 100 nm

(initiator)

CPI-100P: A photocationic polymerization initiator, "CPI (registered trademark)-100P" manufactured by San Apro Corporation.

[Used jigs and devices]

(write)

Untreated glass: 1 mm thick, "S9112" manufactured by Matsunami Glass Ind., Ltd.

(mask)

The following photomasks (No. 1-7) which have the pattern shape shown in FIGS.

No. 1: Square or square dot, 250 μmХ250 μm square-shaped light-shielding parts regularly arranged vertically and horizontally at 250 μm intervals (5-inch glass mask manufactured by Tokyo Process Service Co., Ltd.) )

No. 2: A photomask with square or square dots, a 50 μmХ50 μm square-shaped light-shielding part regularly arranged vertically and horizontally at 150 μm intervals (5-inch glass mask manufactured by Tokyo Process Services Co., Ltd.)

No. 3: Photomask with square or square dots, 100 μmХ100 μm square-shaped light-shielding parts arranged vertically and horizontally at intervals of 100 μm (5-inch glass mask manufactured by Tokyo Process Services Co., Ltd.)

No. 4: Photomask with square or square dots, square-shaped light-shielding portions of 50 μmХ50 μm in size are regularly arranged vertically and horizontally at intervals of 50 μm (5-inch glass mask manufactured by Tokyo Process Services Co., Ltd.)

No. 5: Line or line and space (L/S), a photomask with 100 μm wide line-shaped light blocking portions regularly arranged at intervals of 100 μm (5-inch glass mask manufactured by Tokyo Process Services Co., Ltd.)

No. 6: Photomask with grid-like, 100 μmХ100 μm square transmissive parts arranged vertically and horizontally at intervals of 100 μm (5-inch glass mask manufactured by Tokyo Process Services Co., Ltd.)

No. 7: A photomask (5-inch glass mask manufactured by Tokyo Process Services Co., Ltd.) in which square or square dots, 100 μmХ100 μm square-shaped light-shielding portions are regularly arranged in a checkerboard shape.

(Device)

Bar coater: Daiichirika Co., Ltd. 8 φХ300 mm

Spot UV device: “LC8” manufactured by Hamamatsu Photonics K.K.

Digital microscope: "KH-8700" manufactured by Hirox Co., Ltd.

[Assessment Methods]

(curable)

The following criteria evaluated sclerosis|hardenability of the obtained film.

○·· Full curing after UV irradiation (2nd or 3rd layer)

△... Not completely cured after UV irradiation (2nd or 3rd stage), but fully cured after annealing

Х·· Not fully hardened even after annealing.

(Filler controllability)

From the CCD observation image with a digital microscope, the controllability of the dielectric filler in the obtained film was evaluated relatively according to the following criteria.

◎··· Small amount of filler remaining in the non-agglomerated part

○·· Among the remaining amount of filler in the non-agglomerated part

△... Residual amount of filler in non-agglomerated areas vs.

Х··· No transfer of mask pattern.

(permittivity)

As a pretreatment step, platinum was deposited in a circular shape with a diameter of 40 mm on both sides so that the center was the same on the film for which the dielectric constant was measured with an ion sputtering device (“MC1000” manufactured by Hitachi High-Tech Corporation). . With respect to the pretreated film, the dielectric constant (relative dielectric constant) was measured under the following conditions, and the relative value with respect to the corresponding comparative example was made into the increase degree.

Standard: Conforms to JIS C2138

Permittivity measuring device: Cencept42 (manufactured by Novocontrol Technologies)

Temperature and Humidity: 23℃, 50% RH

Electrode shape: Circular electrode without guide ring (diameter 40 mm)

Electrode arrangement: Align the center of the test piece with the center of the electrode

Test voltage: 1.0 V

Test frequency: 10 Hz to 1 MHz.

(flexibility)

The film having the obtained coating layer was wound around a glass rod having a diameter of 5 mm, the flexibility was evaluated, and the unbreakable film was designated as "○".

[Comparative Examples 1-2]

Each component was mixed and stirred at the ratios shown in Table 1 to prepare a liquid precursor containing a cationically polymerizable compound, a dielectric filler, and an initiator. The prepared liquid precursor was coated on a glass substrate using a bar coater to form a coating film. The obtained coating film was irradiated with ultraviolet light (wavelength 365 nm) without intervening a mask under the conditions (illuminance, irradiation time) described in Table 1 using a spot UV device, and then increased the illuminance again without interposing a mask. Ultraviolet light was irradiated, and the film which has a coating layer of the film thickness described in Table 1 was prepared.

[Examples 1-4]

Each component was mixed and stirred at the ratios shown in Table 1 to prepare a liquid precursor containing a cationically polymerizable compound, a dielectric filler, and an initiator. The prepared liquid precursor was coated on a glass substrate using a bar coater to form a coating film. The obtained coating film was irradiated with ultraviolet light (wavelength 365 nm) through a mask under the conditions (illuminance, irradiation time) described in Table 1 using a spot UV apparatus (1st stage), and then without interposing a mask The ultraviolet light was rapidly irradiated (2nd stage|paragraph), and the film which has a coating layer of the film thickness shown in Table 1 was prepared.

[Examples 5-18]

Each component was mixed and stirred at the ratios shown in Table 1 to prepare a liquid precursor containing a cationically polymerizable compound, a dielectric filler, and an initiator. The prepared liquid precursor was coated on a glass substrate using a bar coater to form a coating film. The obtained coating film was irradiated with ultraviolet light (wavelength 365 nm) through a mask under the conditions (illuminance, irradiation time) described in Table 1 using a spot UV apparatus (1st stage), and then without interposing a mask UV light was rapidly irradiated (2nd stage), the illuminance was raised again, and ultraviolet light was irradiated without interposing a mask (3rd stage), and the film which has the coating layer of the film thickness shown in Table 1 was prepared.

Table 1 shows the evaluation results of the films obtained in Comparative Examples 1-2 and Examples 1-18.

In addition, the CCD photograph of the obtained film is shown to FIGS. 5-24. In addition, on the surface observation image, the filler aggregation part appears black (dark color) because of observation by transmitted light.

As is clear from the results in Table 1, the films of Examples were excellent in curability, and the dielectric filler was also sufficiently controlled.

[Comparative Example 3]

Each component was mixed and stirred in the ratio shown in Table 2, and the liquid precursor containing a cationically polymerizable compound and an initiator was prepared. The prepared liquid precursor was coated on a glass substrate using a bar coater to form a coating film. The obtained coating film was irradiated with ultraviolet light (wavelength 365 nm) without a mask under the conditions (illuminance, irradiation time) shown in Table 2 using a spot UV device, and a coating layer having the thickness shown in Table 2 A film with

[Comparative Examples 4 to 7]

Each component was mixed and stirred at the ratios shown in Table 2 to prepare a liquid precursor containing a cationically polymerizable compound, a dielectric filler, and an initiator. The prepared liquid precursor was coated on a glass substrate using a bar coater to form a coating film. The obtained coating film was irradiated with ultraviolet light (wavelength 365 nm) without intervening a mask under the conditions (illuminance, irradiation time) described in Table 2 using a spot UV device, and then raising the illuminance again without interposing a mask Ultraviolet light was irradiated, and the film which has a coating layer of the film thickness shown in Table 2 was prepared.

[Examples 19-29]

Each component was mixed and stirred at the ratios shown in Table 2 to prepare a liquid precursor containing a cationically polymerizable compound, a dielectric filler, and an initiator. The prepared liquid precursor was coated on a glass substrate using a bar coater to form a coating film. The obtained coating film was irradiated with ultraviolet light (wavelength 365 nm) through a mask under the conditions (illuminance, irradiation time) described in Table 2 using a spot UV apparatus (1st stage), and then without interposing a mask UV light was rapidly irradiated (2nd stage), the illuminance was raised again, and ultraviolet light was irradiated without interposing a mask (3rd stage), and the film which has a coating layer of the film thickness shown in Table 2 was prepared.

Table 2 shows the evaluation results of the films obtained in Comparative Examples 3 to 7 and Examples 19 to 29. Moreover, the CCD photograph of the obtained film is shown to FIGS. 25-39.

As is clear from the results in Table 2, the films of Examples were excellent in curability, the dielectric filler was sufficiently controlled, and the dielectric constant was improved. Although the relative value with respect to the comparative example is shown about the dielectric constant, in the Example, the dielectric constant increased by 20% or more compared with the comparative example. Further, the dielectric film obtained in Examples did not crack even when wound around a glass rod having a diameter of 5 mm, and was excellent in flexibility.

The molded article of the present disclosure can be used as a dielectric used for various electric/electronic devices, transportation devices, and the like, and is particularly suitable as a dielectric used as a passive element component such as a capacitor (capacitor), a resistor, an inductor, and the like. Among them, the film-like molded article is also excellent in flexibility, so it is very suitable as a dielectric film (a high dielectric constant insulating film), and is particularly suitable as a film capacitor for household appliances, vehicle-mounted electronic equipment, industrial equipment, power electronics equipment, and the like.

1: agglomeration
1a: Central Station (central part, near central or first area)
1b: mid-region (middle, mid-region or second region)
1c: peripheral region (peripheral portion, near interface, or third region)
2: Non-agglomerate
3: interface
4: the center of the aggregation part

Claims (15)

It contains a resin and a dielectric filler, and is formed of an agglomerated portion, which is an area in which the dielectric filler aggregates, and a non-agglomerated portion, which is a region other than the aggregated portion. A molded article that gradually decreases toward the interface at least in the vicinity of the interface. The molded article according to claim 1, wherein the resin is a cured product of a photocurable resin. The molded article according to claim 2, wherein the photocurable resin is a cationically polymerizable compound. The molded article according to any one of claims 1 to 3, wherein the dielectric filler is an inorganic filler formed of a titanium-containing composite metal oxide. The molded article according to any one of claims 1 to 4, wherein the ratio of the dielectric filler is 0.1 to 100 parts by mass based on 100 parts by mass of the resin. The molded article according to any one of claims 1 to 5, which is in the form of a film. The molded article according to claim 6, wherein the plurality of aggregated portions form a pattern shape and at least one aggregated portion of the plurality of aggregated portions extends in the thickness direction and penetrates through the plurality of aggregated portions. The molded body according to any one of claims 1 to 7, which is a dielectric film. 9. The molded article according to any one of claims 1 to 8, comprising an agglomeration step of aggregating the dielectric filler by applying active energy to a partial region of the liquid precursor containing the resin precursor and the dielectric filler to obtain a precursor molded article. manufacturing method. 10. The method according to claim 9, comprising a polymerization completion step of imparting active energy to an uncured region of the precursor molded body that has undergone the agglomeration step to complete polymerization. The production method according to claim 9 or 10, wherein the liquid precursor contains a photoacid generator, and the activation energy is actinic light. The molded object obtained by the manufacturing method in any one of Claims 9-11. A liquid precursor comprising a photocurable resin and a dielectric filler, the liquid precursor for forming a molded article having an agglomerated portion that is a region in which the dielectric filler aggregates and a non-agglomerated portion that is a region other than the agglomerated portion, and contains a photocurable resin and a dielectric filler liquid precursor. A joined body in which a substrate formed of a resin, ceramic or metal and the molded article according to any one of claims 1 to 8 and 12 are joined. 15. The assembly according to claim 14, which is a capacitor.

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