JP6555975B2 - New imine group-containing resin - Google Patents

Description

  The present invention relates to a novel imine group-containing resin. The present invention also relates to a thermosetting molding material containing the imine group-containing resin. Furthermore, the present invention relates to a resin molded product and a semiconductor encapsulant formed from the thermosetting molding material.

In recent years, as electronic products have been improved in performance, further improvements have been required in the characteristics of resins used in the products.
For example, a polyhydric hydroxy resin obtained by cross-linking phenols with biphenyls for the purpose of reducing water absorption in order to improve heat resistance and prevent cracks caused by rapid vaporization and expansion of moisture absorption A resin obtained by curing an epoxy resin has been proposed (Patent Document 1). Such a resin has improved flame retardancy and a low water absorption as compared with a general novolac resin, but a sufficiently high glass transition temperature is not obtained.

  On the other hand, a resin obtained by curing a polyhydric hydroxy resin obtained by crosslinking phenols and polyhydric phenols with biphenyls and an epoxy resin has been proposed (Patent Document 2). Such resins have improved crosslink density by incorporating polyhydric phenols such as resorcin and catechol into the structure. In this resin, while achieving a high glass transition temperature, the water absorption increases and the thermal decomposition temperature also decreases.

  Therefore, a resin having all the required performances of high glass transition temperature, high pyrolysis temperature and low water absorption at the same time has not yet been found.

JP 7-239473 A JP 2013-43958 A

  An object of the present invention is to provide a resin having a high glass transition temperature, a high thermal decomposition temperature, and a low water absorption rate.

  In light of the situation where improvements in various properties are required in recent high-performance electronic products, the present inventors have eagerly investigated whether these properties can be realized by another curing system that is not an epoxy curing system. It was found that by using a resin-amine curing system, a resin having a high glass transition temperature, a high thermal decomposition temperature and a low water absorption rate can be obtained, and the present invention has been completed.

［式中、Ｙは、炭素原子数１〜４のアルコキシル基またはハロゲン原子を表し；
Ｒ_１及びＲ_２は、存在する場合は、各々独立に、炭素数が１〜４のアルキル基を表し；
ｓ及びｔは、各々独立して、１〜３の整数を表す。］
で表される化合物および以下の式（ＩＩ）：

［式中、Ｚは、炭素原子数１〜４のアルコキシル基またはハロゲン原子を表し；
Ｒ_３は、存在する場合は、炭素数が１〜４のアルキル基を表し；
ｖは、２〜６の整数を表す。］
で表される化合物からなる群より選択される架橋剤とを反応して得られるアルデヒド含有樹脂、並びに、
モノアミン類
を反応させて得られたイミン基含有樹脂；
［２］ 以下の構造単位（Ａ）及び（Ｂ）：

［式中、
^＊１及び^＊２は、各々、結合手を示し、
ここで、^＊１は、いずれかの^＊２と結合し、
^＊１と^＊１同士、^＊２と^＊２同士は結合することができず、
構造単位（Ｂ）の^＊２は、^＊１と結合しない場合は水素を示し、
構造単位（Ａ）は、ポリマー鎖末端の一方を示し、１つのポリマー鎖に一単位存在する：
Ｒは、−ＣＨ_２−であるか、以下の式（ＩＩＩ）：

（ここで、Ｒ_１及びＲ_２は、存在する場合は、各々独立に、炭素数が１〜４のアルキル基を表す。）
で表されるか、若しくは以下の式（ＩＶ）：

（ここで、Ｒ_３は、存在する場合は、炭素数が１〜４のアルキル基を表す。）
で表される。］
からなるポリマー鎖、及び／又は構造単位（Ｂ）からなる環状ポリマーを含むアルデヒド含有樹脂、並びに、
モノアミン類
を反応させて得られたイミン基含有樹脂；
［３］ 前記フェノール性水酸基を持つヒドロキシアルデヒドモノマーがオルソヒドロキシベンズアルデヒドであり、前記架橋剤が式（Ｉ）で表される化合物である、前記［１］に記載のイミン基含有樹脂；
［４］ 前記フェノール性水酸基を持つヒドロキシアルデヒドモノマーがオルソヒドロキシベンズアルデヒドであり、前記架橋剤が式（ＩＩ）で表される化合物である、前記［１］に記載のイミン基含有樹脂；
［５］ 構造単位（Ａ）及び（Ｂ）においてアルデヒド基がオルソ位にあり、Ｒが式（ＩＩＩ）で表される、前記［２］に記載のイミン基含有樹脂；
［６］ 構造単位（Ａ）及び（Ｂ）においてアルデヒド基がオルソ位にあり、Ｒが式（ＩＶ）で表される、前記［２］に記載のイミン基含有樹脂；
［７］ 前記モノアミン類が、アリルアミンである、前記［１］〜［６］のいずれか１項に記載のイミン基含有樹脂；
［８］ 前記［１］〜［７］のいずれか１項に記載のイミン基含有樹脂を含む、熱硬化性成形材料；
［９］ 前記［８］記載の熱硬化性成形材料から形成される樹脂成形物；
［１０］ 前記［８］に記載の熱硬化性成形材料から形成される半導体封止材
を提供するものである。 That is, the present invention
[1] Hydroxyaldehyde monomer having phenolic hydroxyl group and formaldehyde, the following formula (I):

[Wherein Y represents an alkoxyl group having 1 to 4 carbon atoms or a halogen atom;
R ₁ and R ₂ , if present, each independently represents an alkyl group having 1 to 4 carbon atoms;
s and t each independently represent an integer of 1 to 3. ]
And the following formula (II):

[Wherein Z represents an alkoxyl group having 1 to 4 carbon atoms or a halogen atom;
R ₃ , if present, represents an alkyl group having 1 to 4 carbon atoms;
v represents an integer of 2 to 6. ]
An aldehyde-containing resin obtained by reacting with a crosslinking agent selected from the group consisting of compounds represented by:
An imine group-containing resin obtained by reacting monoamines;
[2] The following structural units (A) and (B):

[Where:
^* 1 and ^* 2 each represent a bond,
Where ^* 1 is combined with any ^* 2
^* 1 and ^* 1, and ^* 2 and ^* 2 cannot be combined,
^* 2 in the structural unit (B) represents hydrogen when not bonded to ^* 1,
The structural unit (A) represents one of the polymer chain ends, and one unit exists in one polymer chain:
R is —CH ₂ — or the following formula (III):

(Here, R ₁ and R ₂ , if present, each independently represents an alkyl group having 1 to 4 carbon atoms.)
Or the following formula (IV):

(Here, R ₃ , if present, represents an alkyl group having 1 to 4 carbon atoms.)
It is represented by ]
An aldehyde-containing resin comprising a polymer chain comprising: and / or a cyclic polymer comprising a structural unit (B); and
An imine group-containing resin obtained by reacting monoamines;
[3] The imine group-containing resin according to [1], wherein the hydroxyaldehyde monomer having a phenolic hydroxyl group is orthohydroxybenzaldehyde, and the crosslinking agent is a compound represented by the formula (I);
[4] The imine group-containing resin according to [1], wherein the hydroxyaldehyde monomer having a phenolic hydroxyl group is orthohydroxybenzaldehyde, and the crosslinking agent is a compound represented by the formula (II);
[5] The imine group-containing resin according to the above [2], wherein the aldehyde group is in the ortho position in the structural units (A) and (B), and R is represented by the formula (III);
[6] The imine group-containing resin according to [2], wherein the aldehyde group is in the ortho position in the structural units (A) and (B), and R is represented by the formula (IV);
[7] The imine group-containing resin according to any one of [1] to [6], wherein the monoamines are allylamine;
[8] A thermosetting molding material containing the imine group-containing resin according to any one of [1] to [7];
[9] A resin molded product formed from the thermosetting molding material according to [8];
[10] A semiconductor encapsulant formed from the thermosetting molding material according to [8] is provided.

According to the present invention, a resin having a high glass transition temperature, a high thermal decomposition temperature, and a low water absorption rate can be provided.
The resin molded product obtained from the resin of the present invention has a high glass transition temperature, a high thermal decomposition temperature, and a low water absorption rate. Therefore, the resin molded product is extremely useful as a highly functional polymer material. Excellent materials such as semiconductor encapsulants, electrical insulation materials, copper-clad laminate resins, resists, electronic component encapsulation resins, liquid crystal color filter resins, paints, various coating agents, adhesives, build-up laminates It can be used for a wide range of applications such as plate materials and FRP.

［式中、Ｙは、炭素原子数１〜４のアルコキシル基またはハロゲン原子を表し；
Ｒ_１及びＲ_２は、存在する場合は、各々独立に、炭素数が１〜４のアルキル基を表し；
ｓ及びｔは、各々独立して、１〜３の整数を表す。］
で表される化合物、及び以下の式（ＩＩ）：

［式中、Ｚは、炭素原子数１〜４のアルコキシル基またはハロゲン原子を表し；
Ｒ_３は、存在する場合は、炭素数が１〜４のアルキル基を表し；
ｖは、２〜６の整数を表す。］
で表される化合物からなる群より選択される架橋剤とを反応して得られるアルデヒド含有樹脂、並びに、
モノアミン類
を反応させて得られたイミン基含有樹脂である。 One embodiment of the present invention comprises a hydroxyaldehyde monomer having a phenolic hydroxyl group and formaldehyde, the following formula (I):

[Wherein Y represents an alkoxyl group having 1 to 4 carbon atoms or a halogen atom;
R ₁ and R ₂ , if present, each independently represents an alkyl group having 1 to 4 carbon atoms;
s and t each independently represent an integer of 1 to 3. ]
And the following formula (II):

[Wherein Z represents an alkoxyl group having 1 to 4 carbon atoms or a halogen atom;
R ₃ , if present, represents an alkyl group having 1 to 4 carbon atoms;
v represents an integer of 2 to 6. ]
An aldehyde-containing resin obtained by reacting with a crosslinking agent selected from the group consisting of compounds represented by:
It is an imine group-containing resin obtained by reacting monoamines.

The hydroxy aldehyde monomer having a phenolic hydroxyl group is not particularly limited as long as it is a monomer having both substituents (phenolic hydroxyl group and aldehyde group). For example, monohydroxy such as orthohydroxybenzaldehyde, parahydroxybenzaldehyde, metahydroxybenzaldehyde and the like. Benzaldehydes, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, dihydroxybenzaldehydes such as 3,4-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,4, Trihydroxybenz such as 5-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde Aldehyde compounds, 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, naphthaldehyde and the like, such as 6-hydroxy-2-naphthaldehyde and the like.
In the present invention, monohydroxybenzaldehydes such as orthohydroxybenzaldehyde, parahydroxybenzaldehyde, metahydroxybenzaldehyde and the like are preferable, and orthohydroxybenzaldehyde is particularly preferable.
When orthohydroxybenzaldehyde is used as the monomer, the reactivity with the cross-linking agent is good, and the monomer remaining in the reaction can be easily recovered and recycled.

  The aldehyde-containing resin can be obtained by reacting a hydroxyaldehyde monomer with a crosslinking agent selected from the group consisting of formaldehyde, a compound represented by formula (I) and a compound represented by formula (II). .

Formaldehyde may be used in solid form or in an aqueous solution. However, since solid formaldehyde has low water content and high reactivity with hydroxyaldehyde monomers, it is preferable to use solid formaldehyde. .
Although the reaction may be carried out while dehydrating using formaldehyde in an aqueous solution, formaldehyde may distill out and the molar ratio may change.

で表される化合物について説明する。
式中、Ｙは、炭素原子数１〜４のアルコキシル基またはハロゲン原子を表す。
アルコキシル基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、ｉ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔ−ブトキシ基等が挙げられ、好ましくはメトキシ基である。
ハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられ、好ましくは、塩素、臭素である。 Next, the formula (I):

The compound represented by these is demonstrated.
In formula, Y represents a C1-C4 alkoxyl group or a halogen atom.
Examples of the alkoxyl group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, and a t-butoxy group, preferably a methoxy group is there.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.

In formula (I), R ₁ and R ₂ may or may not be present, and when present, each independently represents an alkyl group having 1 to 4 carbon atoms. R ₁ and R ₂ may be the same or different.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and the like.
R ₁ and R ₂ , if present, can each be present in the range of 1 to 4 on each benzene ring.
Further, R ₁ is, if there are two or more on the benzene ring, each R ₁ may be the same or different. Similarly, when two or more R ₂ are present on the benzene ring, each R ₂ may be the same or different.

  In formula (I), s and t each independently represent an integer of 1 to 3. Preferably, s and t are 1.

  The compound represented by the formula (I), ie, bis (alkoxymethyl) biphenyl or bis (halogenated methyl) biphenyl is an isomer of 4,4′-form, 2,2′-form, and 2,4′-form However, it is preferably a 4,4′-isomer that is relatively inexpensive and has good reactivity with the hydroxyaldehyde monomer.

で表される化合物は、式中、Ｚは、炭素原子数１〜４のアルコキシル基またはハロゲン原子を表す。
アルコキシル基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、ｉ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔ−ブトキシ基等が挙げられ、好ましくはメトキシ基である。
ハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられ、好ましくは、塩素、臭素である。 Formula (II):

In the formula, Z represents an alkoxyl group having 1 to 4 carbon atoms or a halogen atom.
Examples of the alkoxyl group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, and a t-butoxy group, preferably a methoxy group is there.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.

In formula (II), R ₃ may or may not be present, and when present, represents an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and the like.
R ₃ , if present, can be present in the range of 1 to 4 on each benzene ring.
Furthermore, R ₃ is, if there are two or more on the benzene ring, each R ₃ may be the same or different.

  In formula (II), v represents an integer of 2 to 6. Preferably v is 2.

  The compound represented by the formula (II), that is, bis (alkoxymethyl) xylene or bis (halogenated methyl) xylene is an isomer of 4,4′-isomer, 2,2′-isomer, and 2,4′-isomer. However, it is preferably a 4,4′-isomer that is relatively inexpensive and has good reactivity with the hydroxyaldehyde monomer.

  In the present invention, the molar ratio of the crosslinking agent to the hydroxyaldehyde monomer (crosslinking agent / monomer) is usually 0.01 to 0.99, preferably 0.05 to 0.60. When the molar ratio is lower than the above range, the yield is reduced. On the other hand, when the molar ratio is higher than the above range, the reaction between the hydroxyaldehyde monomer and the crosslinking agent takes time, which is not preferable in productivity.

In the present invention, a catalyst can be added when the hydroxyaldehyde monomer and the crosslinking agent are reacted. Catalysts include inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, boron trifluoride, etc.), organic acids (oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, etc.), alkali metals (aluminum chloride) , Iron chloride, zinc chloride) can be used, and there are no particular restrictions on these types as long as the reaction proceeds.
When bis (halogenated methyl) biphenyl is used as a crosslinking agent, the reaction can be performed without adding a catalyst.

  The addition amount of the catalyst is usually 0.01 to 10% by mass, preferably 0.10 to 1.00% by mass, based on the hydroxyaldehyde monomer. When the addition amount of the catalyst is less than the above range, the reaction rate is slow, and when it is more than the above range, the reaction proceeds rapidly and it becomes difficult to control the reaction.

  The temperature at which the hydroxyaldehyde monomer and the crosslinking agent are reacted is usually 10 to 250 ° C, preferably 60 to 200 ° C. When the reaction temperature is lower than the above range, the reaction does not proceed. When the reaction temperature is higher than the above range, it becomes difficult to control the reaction, and the target aldehyde-containing resin cannot be obtained stably.

When the hydroxyaldehyde monomer is reacted with the crosslinking agent, the reaction may be performed under normal pressure or under pressure.
In addition, when formaldehyde is used as the crosslinking agent, the reactivity with the hydroxy aldehyde monomer is poor, so that unreacted formaldehyde may distill out of the system during the initial reaction. Therefore, it is preferable to carry out the pressure reaction in terms of suppressing distillation of formaldehyde and improving the reaction rate.

  In the present invention, it is preferable to remove the unreacted hydroxyaldehyde monomer after reacting the hydroxyaldehyde monomer with the crosslinking agent. When a considerable amount of unreacted hydroxyaldehyde monomer is contained in the aldehyde-containing resin, monoamines preferentially react with the hydroxyaldehyde monomer over the aldehyde-containing resin when preparing a resin molding or the like from the resin varnish described later. This is not preferable because the curing reaction of the aldehyde-containing resin is hindered. In the present invention, the aldehyde-containing resin preferably contains 1% or less, more preferably 0.1% or less of an unreacted hydroxyaldehyde monomer.

からなるポリマー鎖、及び／又は構造単位（Ｂ）からなる環状ポリマーを含むアルデヒド含有樹脂、並びに、
モノアミン類
を反応させて得られたイミン基含有樹脂である。 Another embodiment of the present invention is the following structural units (A) and (B):

An aldehyde-containing resin comprising a polymer chain comprising: and / or a cyclic polymer comprising a structural unit (B); and
It is an imine group-containing resin obtained by reacting monoamines.

In the structural units (A) and (B), ^* 1 and ^* 2 each represent a bond. Here, ^* 1 is combined with any ^* 2. Also, ^* 1 and ^* 1, and ^* 2 and ^* 2 cannot be combined. Further, ^* 2 in the structural unit (B) represents hydrogen when not bonded to ^* 1. The structural unit (A) represents one end of the polymer chain, and one unit exists in one polymer chain.

（ここで、Ｒ_１及びＲ_２は、式（Ｉ）において定義した通りである。）
で表されるか、又は以下の式（ＩＶ）：

（ここで、Ｒ_３は、式（ＩＩ）において定義した通りである。）
で表される。 R is —CH ₂ — or the following formula (III):

(Here, R ₁ and R ₂ are as defined in Formula (I).)
Or the following formula (IV):

(Here, R ₃ is as defined in formula (II).)
It is represented by

An aldehyde-containing resin containing a polymer chain composed of structural units (A) and (B) and / or a cyclic polymer composed of structural unit (B) is a hydroxyaldehyde monomer having a phenolic hydroxyl group, formaldehyde, and a compound of formula (I) And a crosslinking agent selected from the group consisting of the compound represented by formula (II) and the compound represented by formula (II).
In the structural units (A) and (B), the aldehyde group is preferably in the ortho position.
When the hydroxyaldehyde monomer is orthohydroxybenzaldehyde or parahydroxybenzaldehyde, there are two reactive sites, one of ^* 2 in the structural unit (B) is a bond, and the other is hydrogen. When the hydroxyaldehyde monomer is metahydroxybenzaldehyde, there are three reaction points, and both ^* 2 in the structural unit (B) can be bonds, but depending on conditions, one is a bond and the other is a bond. In some cases, hydrogen or both are hydrogen.

  The aldehyde-containing resin containing a polymer chain composed of the structural units (A) and (B) and / or a cyclic polymer composed of the structural unit (B) is preferably 1% or less of unreacted hydroxyaldehyde monomer, more preferably Contains 0.1% or less.

As monoamines, there is no particular problem as long as it contains one amino group in the structure, but amines containing benzene rings such as allylamine, benzylamine, aniline, toluidine, anisidine, aminobenzonitrile, methylamine, Examples include alkylamines such as ethylamine, etheramines having an ether bond, and the like.
In the present invention, allylamine is preferably used. Although not intended to be bound by theory, when allylamine is used as a monoamine, allyl groups are polymerized to give high heat resistance to the resin molded product.

（式中、ｎは１〜３０の整数であり、Ｒは上述した通りである）
で表される。 When allylamine is used as the monoamine, the imine group-containing resin of the present invention has, for example, the following formula:

(In the formula, n is an integer of 1 to 30, and R is as described above).
It is represented by

  Aldehyde-containing resins and monoamines react, for example, at a monoamine equivalent / aldehyde equivalent resin ratio (molar ratio) of 0.5 to 1.5. Further, the reaction preferably takes place at a monoamine equivalent / aldehyde equivalent resin ratio of 0.9 to 1.1. By reacting at an equivalent ratio within the above range, excellent heat resistance can be imparted to the resulting cured product. Furthermore, since no excess monoamines are used, the productivity is excellent.

  The reaction between the aldehyde-containing resin and the monoamines is not particularly limited as long as the reaction is performed at a temperature at which they react. Aldehyde-containing resins and monoamines usually react in a temperature range of 10 to 150 ° C, preferably in a temperature range of 30 to 90 ° C. By reacting in the above temperature range, the reaction can be carried out below the boiling point of monoamine, and the production stability is excellent.

Another embodiment of the present invention relates to a resin composition comprising the imine group-containing resin.
Yet another embodiment of the present invention relates to a thermosetting molding material containing the imine group-containing resin. In addition to the imine group-containing resin, a filler, a curing catalyst, a coupling agent, a wax, a flame retardant, and the like may be added to the resin composition and the thermosetting molding material.

  As filler, fused silica, crystalline silica, silica gel, porous silica, glass, zeolite, alumina, calcium carbonate, calcium oxide, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon , Fine particles such as fosterite, steatite, spinel, mullite, titania, talc, clay, mica, or the like in the form of spheres. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. One of these inorganic fillers may be used alone, or two or more thereof may be used in combination.

  Examples of the curing catalyst include cycloamidine compounds such as diazabicycloalkene such as 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7, Derivatives thereof, phenol novolac salts thereof and these compounds to maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2 , 3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, quinone compounds such as phenyl-1,4-benzoquinone, and compounds having a π bond such as diazophenylmethane. Compound with intramolecular polarization, triethylenediamine, benzyldimethylamine, triethanol Tertiary amines such as amine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, etc. Tetrasubstituted phosphonium / tetrasubstituted borates such as imidazoles, tetraphenylphosphonium / tetraphenylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, and triphenyl Phosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, Lis (dialkylphenyl) phosphine, Tris (trialkylphenyl) phosphine, Tris (tetraalkylphenyl) phosphine, Tris (dialkoxyphenyl) phosphine, Tris (trialkoxyphenyl) phosphine, Tris (tetraalkoxyphenyl) phosphine, Trialkylphosphine And organic phosphines such as dialkylarylphosphine and alkyldiarylphosphine.

  As a coupling agent, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ- Anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) amino Propyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) ) Silane coupling agents such as -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyltriisostearoyl titanate, isopropyltris (Dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphate) Ite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate , Titanate cups such as isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate Ring agents, etc. are listed. Even if these are used alone, two or more types are combined It may be used to.

  Examples of the wax include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene, etc. The seeds may be used alone or in combination of two or more.

  Another embodiment of the present invention is a resin molded product that can be formed from the thermosetting material.

  The resin molded product includes a resin molded product. The resin molding can be prepared, for example, by molding a thermosetting material at 80 to 200 ° C. by transfer, and after baking at 150 to 250 ° C. for 1 to 5 hours. The resin molded product formed by such a method is, for example, a semiconductor sealing material.

  In the imine group-containing resin of the present invention, by using no epoxy curing, the crosslink density is improved and a high glass transition temperature is realized. Moreover, since epoxy curing is not used, the water absorption rate of the resin can be reduced. Furthermore, since thermal decomposition derived from epoxy can be suppressed, a high thermal decomposition temperature is realized.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.
[Measurement method and measurement equipment]
About the resin obtained by the synthesis example mentioned later, molecular weight Mw, dispersion degree Mw / Mn, the softening point, and melt viscosity were measured with the following method.
(1) Molecular weight Mw and degree of dispersion Mw / Mn
GPC measuring device: HLC8120GPC manufactured by Tosoh Corporation
Column: TSKgel G3000H + G2000H + G2000H
(2) Softening point The softening point was measured according to JIS K6910.
(3) Melt Viscosity The melt viscosity at 150 ° C. was measured with a viscometer (CAP2000 VISCOMETER manufactured by Brookfield) set at 150 ° C.

About the resin molding obtained in the Example mentioned later, the glass transition temperature, the thermal decomposition temperature, and the water absorption were measured with the following method.
(4) Glass transition temperature The resin molded product was processed into a width of 1.0 mm, a length of 5.5 mm and a thickness of 0.2 mm, and 10 ° C./min using a viscoelastic spectrometer (DMS 110 manufactured by Seiko Instruments Inc.). It measured in the range of 30 to 300 degreeC with the temperature increase rate.
(5) Thermal decomposition temperature The resin molded product was measured for thermal weight loss under an air atmosphere using a differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA 6300 manufactured by Seiko Instruments Inc.), and a 5% thermal decomposition starting temperature was determined.
(6) Water absorption rate Create a test piece for water absorption evaluation (diameter 50 mm, thickness 3 mm) from a thermosetting molding material, put the test piece and pure water (20 ml) prepared in a pressure cooker, and heat at 121 ° C oven Was used to measure the weight increase after 20 hours, and the water absorption was calculated.

[Synthesis Example 1]
Reaction of orthohydroxybenzaldehyde and formaldehyde (molar ratio = 0.40)
850 g (6.967 mol) of orthohydroxybenzaldehyde, 90.9 g (2.788 mol) of 92% paraformaldehyde, and 4.3 g of paratoluenesulfonic acid were placed in a pressure-resistant reaction vessel equipped with a thermometer, a stirrer and a condenser. The mixture was added, heated to 140 ° C. under pressure, and subjected to a pressure reaction for 4 hours. After completion of the pressurization reaction, after cooling to 100 ° C. and releasing the pressurization, the temperature was raised while dehydrating to 140 ° C. at normal pressure. Thereafter, a secondary reaction was carried out at 140 ° C. for 3 hours, and paratoluenesulfonic acid was neutralized with a 30 mass% NaOH aqueous solution. After removing the neutralized salt by washing with water, the unreacted orthohydroxybenzaldehyde monomer was removed to obtain an aldehyde-containing novolak resin.
The obtained resin had a softening point of 58.1 ° C. and a melt viscosity at 150 ° C. of 0.2 P.
The molecular weight Mw was 393 and the dispersity Mw / Mn was 1.25 by gel permeation chromatographic analysis (hereinafter sometimes abbreviated as “GPC”).

[Synthesis Example 2]
Reaction of orthohydroxybenzaldehyde and bismethoxymethylbiphenyl (molar ratio = 0.10)
850 g (6.967 mol) of orthohydroxybenzaldehyde, 168.6 g (0.696 mol) of bismethoxymethylbiphenyl, 8.5 g of paratoluenesulfonic acid (orthohydroxy) in a 1 L internal reaction vessel equipped with a thermometer, stirrer and condenser. 1 wt% with respect to benzaldehyde) was added, the temperature was raised to 160 ° C., and the reaction was carried out for 4 hours. Methanol produced as a by-product in the reaction was removed out of the system. After completion of the reaction, neutralization and washing with water were carried out to remove unreacted orthohydroxybenzaldehyde monomer to obtain an aldehyde-containing biphenyl resin.
The softening point of the obtained resin was 75 ° C., and the melt viscosity at 150 ° C. was 0.6P. According to gel permeation chromatographic analysis, the molecular weight Mw was 648, and the degree of dispersion Mw / Mn was 1.33.

[Synthesis Example 3]
Reaction of orthohydroxybenzaldehyde and bismethoxymethylbiphenyl (molar ratio = 0.40)
850 g (6.967 mol) of orthohydroxybenzaldehyde, 674.5 g (2.787 mol) of bismethoxymethylbiphenyl, 8.5 g of paratoluenesulfonic acid (orthohydroxy) in a 1 L internal reaction vessel equipped with a thermometer, stirrer and condenser. 1 wt% with respect to benzaldehyde) was added, the temperature was raised to 160 ° C., and the reaction was carried out for 4 hours. Methanol produced as a by-product in the reaction was removed out of the system. After completion of the reaction, neutralization and washing with water were carried out to remove unreacted orthohydroxybenzaldehyde monomer to obtain an aldehyde-containing biphenyl resin.
The resulting resin had a softening point of 81 ° C. and a melt viscosity at 150 ° C. of 1.2 P. According to gel permeation chromatographic analysis, the molecular weight Mw was 815, and the degree of dispersion Mw / Mn was 1.48.

[Synthesis Example 4]
Reaction of orthohydroxybenzaldehyde and para-xylene glycol dimethyl ether (molar ratio = 0.10)
850 g (6.967 mol) of orthohydroxybenzaldehyde, 115.5 g (0.696 mol) of paraxylene glycol dimethyl ether, and 8.5 g (ortho of paratoluenesulfonic acid) in a 1 L reaction vessel equipped with a thermometer, stirrer and condenser. 1 wt% relative to hydroxybenzaldehyde) was added, the temperature was raised to 160 ° C., and the reaction was carried out for 4 hours. Methanol produced as a by-product in the reaction was removed out of the system. After completion of the reaction, neutralization and washing with water were carried out to remove unreacted orthohydroxybenzaldehyde monomer to obtain an aldehyde-containing xylylene resin.
The resulting resin had a softening point of 71 ° C. and a melt viscosity at 150 ° C. of 0.5 P. The molecular weight Mw by gel permeation chromatography analysis was 551, and the degree of dispersion Mw / Mn was 1.31.

[Synthesis Example 5]
Reaction of orthohydroxybenzaldehyde and para-xylene glycol dimethyl ether (molar ratio = 0.40)
850 g (6.967 mol) of orthohydroxybenzaldehyde, 462.6 g (2.787 mol) of paraxylene glycol dimethyl ether, and 8.5 g of paratoluenesulfonic acid (ortho) were added to a 1 L internal reaction vessel equipped with a thermometer, a stirrer and a condenser. 1 wt% relative to hydroxybenzaldehyde) was added, the temperature was raised to 160 ° C., and the reaction was carried out for 4 hours. Methanol produced as a by-product in the reaction was removed out of the system. After completion of the reaction, neutralization and washing with water were carried out to remove unreacted orthohydroxybenzaldehyde monomer to obtain an aldehyde-containing xylylene resin.
The resulting resin had a softening point of 80 ° C. and a melt viscosity at 150 ° C. of 1.7 P. The molecular weight Mw by gel permeation chromatography analysis was 756, and the degree of dispersion Mw / Mn was 1.44.

Next, the imine group-containing resin of the present invention was prepared using the aldehyde-containing resin synthesized in the synthesis example.
[Example 1]
Preparation of imine group-containing resin (imine group-containing novolak resin) using aldehyde-containing novolak resin of Synthesis Example 1 100.0 g of the resin synthesized in Synthesis Example 1 was dissolved in 100.0 g of toluene and heated to 80 ° C. . Next, 42.0 g of allylamine was added over 2 hours while paying attention to heat generation. Thereafter, the used toluene was removed at 160 ° C. to obtain a resin A having a softening point of 55 ° C. and a melt viscosity of 0.2 P at 150 ° C. The molecular weight determined by gel permeation chromatography was Mw 433, and the degree of dispersion Mw / Mn was 1.20.

[Example 2]
Preparation of imine group-containing resin (imine group-containing biphenyl resin) using aldehyde-containing biphenyl resin of Synthesis Example 2 100.0 g of the resin synthesized in Synthesis Example 2 was dissolved in 100.0 g of toluene and heated to 80 ° C. Next, 25.4 g of allylamine was added over 2 hours while paying attention to heat generation. Thereafter, the used toluene was removed at 160 ° C. to obtain a resin B having a softening point of 70 ° C. and a melt viscosity of 0.8 P at 150 ° C. The molecular weight Mw by gel permeation chromatography analysis was 688, and the degree of dispersion Mw / Mn was 1.29.

[Example 3]
Preparation of imine group-containing resin (imine group-containing biphenyl resin) using aldehyde-containing biphenyl resin of Synthesis Example 3 100.0 g of the resin synthesized in Synthesis Example 3 was dissolved in 100.0 g of toluene and heated to 80 ° C. Next, 23.4 g of allylamine was added over 2 hours while paying attention to heat generation. Thereafter, the used toluene was removed at 160 ° C. to obtain a resin C having a softening point of 74 ° C. and a melt viscosity of 1.5 P at 150 ° C. The molecular weight Mw by gel permeation chromatography analysis was 889, and the degree of dispersion Mw / Mn was 1.41.

[Example 4]
Preparation of imine group-containing resin (imine group-containing xylylene resin) using aldehyde-containing xylylene resin of Synthesis Example 4 100.0 g of the resin synthesized in Synthesis Example 4 was dissolved in 100.0 g of toluene and heated to 80 ° C. Next, 33.0 g of allylamine was added over 2 hours while paying attention to heat generation. Thereafter, the toluene used was removed at 160 ° C. to obtain a resin D having a softening point of 68 ° C. and a melt viscosity of 0.5 P at 150 ° C. The molecular weight Mw by gel permeation chromatography analysis was 592, and the degree of dispersion Mw / Mn was 1.27.

[Example 5]
Preparation of imine group-containing resin (imine group-containing xylylene resin) using aldehyde-containing xylylene resin of Synthesis Example 5 100.0 g of the resin synthesized in Synthesis Example 5 was dissolved in 100.0 g of toluene and heated to 80 ° C. Next, 31.0 g of allylamine was added over 2 hours while paying attention to heat generation. Thereafter, the used toluene was removed at 160 ° C. to obtain a resin E having a softening point of 72 ° C. and a melt viscosity of 1.3 P at 150 ° C. According to gel permeation chromatographic analysis, the molecular weight Mw was 806, and the degree of dispersion Mw / Mn was 1.40.

[Comparative Example 1]
Preparation of phenol xylene aralkyl resin for general sealing use by reaction of phenol with para-xylene glycol dimethyl ether Thermometer, stirrer, condenser tube with 1L inner volume glass flask equipped with 1L internal capacity phenol 235g (2.5mol), para 166 g (1.0 mol) of xylene glycol dimethyl ether was added, 0.4 g of paratoluenesulfonic acid was added to this solution, and the mixture was reacted at 150 ° C. for 3 hours. Methanol generated at this time was removed out of the system. After completion of the reaction, the reaction mixture was cooled to 95 ° C. and neutralized with a 48% KOH aqueous solution. After removing the unreacted monomer, it was washed with water to obtain a polyvalent hydroxy resin. The obtained resin had a softening point of 69 ° C. and a melt viscosity of 0.9 P. The molecular weight Mw by GPC was 801, and the degree of dispersion Mw / Mn was 1.53.

[Comparative Example 2]
Preparation of phenol biphenyl aralkyl resin for general sealing use by reaction of phenol and bismethoxymethylbiphenyl In a 1 L glass flask equipped with a thermometer, stirrer, and condenser, 376 g (4.0 mol) of phenol, bis 242 g (1.0 mol) of methoxymethylbiphenyl was added, 0.6 g of paratoluenesulfonic acid was added to this solution, and the mixture was reacted at 150 ° C. for 3 hours. Methanol generated at this time was removed out of the system. After completion of the reaction, the reaction mixture was cooled to 95 ° C. and neutralized with a 48% KOH aqueous solution. After removing the unreacted monomer, it was washed with water to obtain a polyvalent hydroxy resin. The obtained resin had a softening point of 69 ° C. and a melt viscosity of 0.9 P. The molecular weight Mw by GPC was 616, and the degree of dispersion Mw / Mn was 1.23.

The prepared resin obtained in each of the above Examples and Comparative Examples was prepared as shown in Table 1 below, and a solid was prepared by hot-melt mixing at 100 ° C. using a biaxial mixing roll (manufactured by Daishin Machinery Co., Ltd.). .
When using the prepared resin obtained in the examples, transfer molding was performed for 3 minutes under the conditions of a pressure of 30 kgf / cm ² and 175 ° C. (TEP12-16 manufactured by Fujiwa), and after baking was performed at 230 ° C. for 1 hour. A test piece of a resin molded product was obtained.
In addition, when the prepared resin obtained in the comparative example was used, transfer molding was performed under the same equipment and conditions as in the example, and after baking, after baking at 180 ° C. for 5 hours, a resin molded specimen was obtained. .

  Table 1 shows the test results relating to the physical properties of the test pieces using the prepared resins obtained in the respective Examples and Comparative Examples together with the preparation used for the test pieces. In addition, regarding each component, the numerical value which does not have the description of a unit in a table | surface represents content, and the unit of this content is g.

As shown in Table 1, the resin molded product obtained from the imine group-containing resin of the present invention had a high glass transition temperature, a high thermal decomposition temperature, and a low water absorption rate.
As described above, the resin molded product of the present invention is extremely useful as a high-functional polymer material, and as a thermally and electrically excellent material, a semiconductor encapsulant, an electrical insulating material, a copper-clad laminate resin, a resist It can be used in a wide range of applications such as resin for sealing electronic parts, resin for color filters of liquid crystals, paints, various coating agents, adhesives, build-up laminate materials, FRP and the like.

Claims (9)

Hydroxyaldehyde monomer having a phenolic hydroxyl group and formaldehyde, the following formula (I):

[Wherein Y represents an alkoxyl group having 1 to 4 carbon atoms or a halogen atom;
R ₁ and R ₂ , if present, each independently represents an alkyl group having 1 to 4 carbon atoms;
s and t each independently represent an integer of 1 to 3. ]
And the following formula (II):

[Wherein Z represents an alkoxyl group having 1 to 4 carbon atoms or a halogen atom;
R ₃ , if present, represents an alkyl group having 1 to 4 carbon atoms;
v represents an integer of 2 to 6. ]
An aldehyde-containing resin obtained by reacting with a crosslinking agent selected from the group consisting of compounds represented by:
Monoamines (wherein the monoamines are allylamine)
Imine group-containing resin obtained by reacting. The following structural units (A) and (B):

[Where:
^* 1 and ^* 2 each represent a bond,
Where ^* 1 is combined with any ^* 2
^* 1 and ^* 1, and ^* 2 and ^* 2 cannot be combined,
^* 2 in the structural unit (B) represents hydrogen when not bonded to ^* 1,
The structural unit (A) represents one of the polymer chain ends, and one unit exists in one polymer chain:
R is —CH ₂ — or the following formula (III):

(Here, R ₁ and R ₂ , if present, each independently represents an alkyl group having 1 to 4 carbon atoms.)
Or the following formula (IV):

(Here, R ₃ represents an alkyl group having 1 to 4 carbon atoms, if present)
It is represented by ]
An aldehyde-containing resin comprising a polymer chain comprising: and / or a cyclic polymer comprising a structural unit (B); and
Monoamines (wherein the monoamines are allylamine)
Imine group-containing resin obtained by reacting.   The imine group-containing resin according to claim 1, wherein the hydroxyaldehyde monomer having a phenolic hydroxyl group is orthohydroxybenzaldehyde, and the crosslinking agent is a compound represented by the formula (I).   The imine group-containing resin according to claim 1, wherein the hydroxyaldehyde monomer having a phenolic hydroxyl group is orthohydroxybenzaldehyde, and the crosslinking agent is a compound represented by the formula (II).   The imine group-containing resin according to claim 2, wherein the aldehyde group is in the ortho position in the structural units (A) and (B), and R is represented by the formula (III).   The imine group-containing resin according to claim 2, wherein the aldehyde group is in the ortho position in the structural units (A) and (B), and R is represented by the formula (IV). The thermosetting molding material containing the imine group containing resin of any one of Claims 1-6 . A resin molded product formed from the thermosetting molding material according to claim 7 . The semiconductor sealing material formed from the thermosetting molding material of Claim 7 .