JP5585083B2 - Flame resistant polyurethane imide resin, resin composition and cured film thereof - Google Patents

Description

  The present invention is a polyurethaneimide resin comprising a soft segment made of polycarbonate polyol and a hard segment having an imide bond or an imide bond and an amide bond, wherein the polycarbonate polyol contains a phosphorus atom in the molecule. The present invention relates to a polyurethaneimide resin having improved flame resistance. The present invention also relates to a resin composition containing the polyurethaneimide resin and a cured film obtained by curing the resin composition.

  As resins having both flexibility and heat resistance, various polyurethane imide resins composed of soft segments derived from polycarbonate polyol and hard segments having imide bonds or imide bonds and amide bonds have been proposed. .

  Patent Document 1 and Patent Document 2 describe a polyurethaneimide resin (modified polyamideimide resin) configured to include a soft segment having a carbonate bond and a hard segment having an amideimide group.

Patent Documents 3 and 4 describe a polyurethaneimide resin (modified polyimide resin) including a soft segment having a carbonate bond and a hard segment having an imide group.
Japanese Patent Laid-Open No. 11-12500 JP 2001-302895 A JP 2002-145981 A JP 2006-307183 A

  These polyurethaneimide resins have excellent properties such as low warpage, electrical insulation, printability, solder resistance, solvent resistance and mechanical strength in addition to flexibility and heat resistance. For example, it is suitably used as an insulating protective film of a flexible substrate. However, these polyurethane imide resins, resin compositions and cured films have room for improvement in flame resistance.

  That is, the object of the present invention is to provide various properties such as flexibility, heat resistance, low warpage, electrical insulation, printability, solder resistance, solvent resistance and mechanical strength required as an insulating protective film of a flexible substrate. It is to provide a polyurethaneimide resin, a resin composition thereof and a cured film having improved flame resistance without deteriorating properties.

  The present invention relates to the following matters.

1. In a polyurethaneimide resin comprising a soft segment made of polycarbonate polyol and a hard segment having an imide bond,
Polycarbonate polyol
Formula: -OCOO-
A structural unit (I) represented by:
Residue A
(However, A represents an n-valent residue obtained by removing n alcoholic hydroxyl groups from a phosphorus compound having at least n alcoholic hydroxyl groups, where n is an integer of 2 or more.)
And a structural unit (II) represented by
A polyurethaneimide resin characterized by being a phosphorus-containing polycarbonate polyol characterized in that the terminal group is an alcoholic hydroxyl group.

  In other words, the polyurethaneimide resin of the present invention is a polyurethaneimide resin configured to include a soft segment formed using a polycarbonate polyol containing a phosphorus atom in the molecule and a hard segment having an imide bond. .

  2. 2. The polyurethaneimide resin as described in 1 above, wherein the phosphorus-containing polycarbonate polyol contains a structural unit represented by the general formula (1).

（式（１）中、Ａ^１は少なくとも２個のアルコール性水酸基を有するリン化合物から２個のアルコール性水酸基を除いた２価の残基を表す。）
３． 前記リン含有ポリカーボネートポリオールの数平均分子量が、５００から１００００であることを特徴とする上記１に記載のポリウレタンイミド樹脂。

(In formula (1), A ¹ represents a divalent residue obtained by removing two alcoholic hydroxyl groups from a phosphorus compound having at least two alcoholic hydroxyl groups.)
3. 2. The polyurethaneimide resin as described in 1 above, wherein the phosphorus-containing polycarbonate polyol has a number average molecular weight of 500 to 10,000.

  4). 3. The polyurethaneimide resin according to 1 or 2 above, wherein the residue A in the phosphorus-containing polycarbonate polyol is represented by the general formula (2).

（式（２）中、Ｒ_１は１価の炭化水素基を表し、Ｒ_２は独立に２価の炭化水素基を表し、前記炭化水素基はいずれも構造中に環状構造を有してもよく、またヘテロ原子を有してもよい。）
５． ハードセグメントが式（Ｈ１）〜（Ｈ４）で表される構造単位からなる群から選ばれたいずれかの構造単位を含むことを特徴とする上記１〜４のいずれかに記載のポリウレタンイミド樹脂。

(In Formula (2), R ₁ represents a monovalent hydrocarbon group, R ₂ independently represents a divalent hydrocarbon group, and each of the hydrocarbon groups may have a cyclic structure in the structure. And may have heteroatoms.)
5. 5. The polyurethane imide resin according to any one of 1 to 4 above, wherein the hard segment contains any structural unit selected from the group consisting of structural units represented by formulas (H1) to (H4).

（式中、Ｄは直接結合、−Ｏ−、−ＣＨ_２−、−ＣＯ−、−ＳＯ_２−のいずれかを表す。）
６． 上記１〜５のポリウレタンイミド樹脂を含有する樹脂組成物。

(In the formula, D represents any of a direct bond, —O—, —CH ₂ —, —CO—, and —SO ₂ —).
6). The resin composition containing the polyurethaneimide resin of said 1-5.

  7). A cured film obtained by curing the resin composition of 6.

  In the present invention, the “polyurethaneimide resin” is a resin (modified polyurethane resin) which is a polyurethane resin and has an imide bond formed in the structure of the hard segment. The “imide bond” is to form an imide ring. The polyurethaneimide resin of the present invention may be one containing “imide bond and amide bond”. The imide bond is preferably formed with an aromatic imide ring formed together with an aromatic ring.

  According to the present invention, it is possible to obtain a polyurethaneimide resin having improved flame resistance in a polyurethaneimide resin comprising a soft segment made of polycarbonate polyol and a hard segment having an imide bond.

  That is, according to the present invention, various properties such as flexibility, heat resistance, low warpage, electrical insulation, printability, solder resistance, solvent resistance, and mechanical strength required as an insulating protective film of a flexible substrate are provided. A polyurethane imide resin, a resin composition thereof, and a cured film having improved combustion resistance without being reduced can be obtained.

  Further, the flame-resistant polyurethane imide resin, the resin composition and the cured film of the present invention are also suitably used as electronic / electrical materials, inks, paints, coating materials, adhesives, belt materials, sealing materials, printing rolls, and the like. be able to.

  In the following description, “a phosphorus compound having at least n alcoholic hydroxyl groups” may be appropriately expressed as a phosphorus compound A (OH) n for the sake of simplicity.

The polyurethane imide resin of the present invention is a polyurethane imide resin comprising a soft segment made of polycarbonate polyol and a hard segment having an imide bond.
Formula: -OCOO-
A structural unit (I) represented by:
Residue A
(However, A represents an n-valent residue obtained by removing n alcoholic hydroxyl groups from a phosphorus compound having at least n alcoholic hydroxyl groups, where n is an integer of 2 or more.)
And a structural unit (II) represented by
A polyurethaneimide resin characterized by being a phosphorus-containing polycarbonate polyol characterized in that the terminal group is an alcoholic hydroxyl group.

  Conventionally, a polyurethane resin is generally obtained by a reaction between a polycarbonate polyol constituting a soft segment and a polyvalent isocyanate constituting a hard segment.

  In the polyurethaneimide resin of the present invention, the soft segment is formed using a polycarbonate polyol (preferably polycarbonate diol), and the hard segment is, for example, (i) a polyisocyanate and a tri- or higher functional polycarboxylic acid or a derivative thereof. A method of forming an imide bond (or an imide bond and an amide bond) on a hard segment by reaction with (ii) a polyisocyanate and a polyol comprising an imide bond (or an imide bond and an amide bond) It is formed by using a method of introducing an imide bond (or an imide bond and an amide bond) into the hard segment by reaction.

  Although the method of forming these hard segments is not limited, the conventionally known method can be suitably employed. The method (i) is described in, for example, Patent Documents 1 to 3, and the method (ii) is described in, for example, Patent Document 4.

The polyurethaneimide resin of the present invention is a polycarbonate polyol constituting a soft segment,
Formula: -OCOO-
A structural unit (I) represented by:
Residue A
(However, A represents an n-valent residue obtained by removing n alcoholic hydroxyl groups from a phosphorus compound having at least n alcoholic hydroxyl groups, where n is an integer of 2 or more.)
And a structural unit (II) represented by
It can be easily obtained by using a phosphorus-containing polycarbonate polyol whose terminal group is an alcoholic hydroxyl group.

The polycarbonate polyol used to constitute the soft segment of the polyurethaneimide resin of the present invention,
Formula: -OCOO-
And a structural unit (II) represented by the residue A, and a structural unit (I) represented by formula (I), that is, a carbonate structural unit (oxycarbonyloxy group).

  Here, the residue A represents an n-valent residue obtained by removing n alcoholic hydroxyl groups from a phosphorus compound {that is, phosphorus compound A (OH) n} having at least n alcoholic hydroxyl groups.

n is an integer of 2 or more, preferably 6 or less, and more preferably 2, 3 and 4. In particular, it is preferable to include a residue A in which n is 2, that is, A ¹ shown below.

  In the case of containing a residue A in which n is 2, the phosphorus-containing polycarbonate polyol has the general formula (1):

で示される構造単位を含有する。ここで、Ａ^１は、少なくとも２つのアルコール性水酸基を有するリン化合物から２つのアルコール性水酸基を除いた２価の残基を表す。

The structural unit shown by is contained. Here, A ¹ represents a divalent residue obtained by removing two alcoholic hydroxyl groups from a phosphorus compound having at least two alcoholic hydroxyl groups.

  Further, when a residue A in which n is 3 or more is contained in the polymer chain, for example, branching occurs in the polymer chain as shown in the following formula.

ここでＡ^２は、少なくとも３つのアルコール性水酸基を有するリン化合物から３つのアルコール性水酸基を除いた３価の残基を表す。

Here, A ² represents a trivalent residue obtained by removing three alcoholic hydroxyl groups from a phosphorus compound having at least three alcoholic hydroxyl groups.

  When A is present in the polymer chain, A is linked to n structural units (I), and when present at the end of the polymer, at least one OH and at least one structural unit (I). To form a terminal alcoholic hydroxyl group.

  Residues A contained in the phosphorus-containing polycarbonate polyol may all be the same or different. If they are different, n may contain a different residue A, and n may be the same or may contain a residue A having a different structure.

  Further, when the phosphorus compound A (OH) n has exactly n alcoholic hydroxyl groups, the residue A itself does not contain an alcoholic hydroxyl group. When the phosphorus compound A (OH) n has more alcoholic hydroxyl groups than n, the residue A itself contains one or more alcoholic hydroxyl groups. In general, it is preferable that the phosphorus compound A (OH) n has exactly n alcoholic hydroxyl groups.

  The phosphorus-containing polycarbonate polyol used in the present invention may optionally contain a residue B derived from a polyol component. Residue B is a residue contained in a polymer bonded to a —OCOO— structural unit in a general polycarbonate, for example, from a polyol used to produce a general polycarbonate, an OH group It is a residue excluding. Usually, it is a divalent residue and may contain a trivalent or higher residue due to the branched structure. When residue B is divalent, structural unit:

が、リン含有ポリカーボネートポリオール中に含まれる。

Is contained in the phosphorus-containing polycarbonate polyol.

  The residue B is specifically a group that is introduced into the phosphorus-containing polycarbonate polyol together with the residue A in the [first method] or [second method] described later.

  The terminal group of the phosphorus-containing polycarbonate polyol is an alcoholic hydroxyl group. Here, the alcoholic hydroxyl group means that the carbon to which the hydroxyl group is directly bonded is an aliphatic carbon, that is, not directly bonded to carbon constituting an aromatic ring member such as a benzene ring. For example, it is bonded to a carbon atom of an aliphatic hydrocarbon group or alicyclic hydrocarbon group. Among the aliphatic hydrocarbon groups or alicyclic hydrocarbon groups, an aromatic group may be included as a structural element other than the carbon atom to which the hydroxyl group is bonded, and the aliphatic hydrocarbon group or alicyclic group. A part of the hydrocarbon group may be substituted with oxygen, sulfur, or nitrogen.

  The alcoholic hydroxyl group is more preferably a hydroxyl group that can be represented by the following chemical formula.

-CX ₂ -OH
(X is each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms.)

  The terminal alcoholic hydroxyl group of the phosphorus-containing polycarbonate polyol is an OH group bonded to the residue A or, if it coexists, an OH group bonded to the residue B derived from the polyol component.

  Accordingly, the phosphorus-containing polycarbonate polyol contains the structural unit (I), the structural unit (II) represented by the residue A, and the residue B as an arbitrary structural unit, and preferably consists essentially of these. And the terminal group has -AOH (ie, an alcoholic hydroxyl group bonded to residue A) and, if residue B is present, has -BOH (ie, an alcoholic hydroxyl group bonded to residue B), preferably Consists essentially of these. Therefore, when both residue A and residue B are divalent, a preferred phosphorus-containing polycarbonate polyol has an alternating repeating structure of residue A or residue B and structural unit (I), and the terminal is -AOH Or -BOH.

  When the phosphorus-containing polycarbonate polyol contains the residue A, flame retardancy is improved. Accordingly, the ratio of residue A / residue B is greater than 0/1, preferably 0.1 / 1 or greater. The ratio of residue A / residue B may be 1/0, that is, residue B may not be present.

  The phosphorus compound A (OH) n is not particularly limited as long as it is a phosphorus compound containing a phosphorus atom and having two or more alcoholic hydroxyl groups. Examples of the compound having two alcoholic hydroxyl groups include a phosphine compound represented by the following general formula (3), an aminophosphonate represented by the general formula (4), and a phosphorus system represented by the general formula (5). A polyol compound etc. are mentioned. Any of those commercially available can be used. Among (3) to (5), the phosphine compound represented by the general formula (3) is preferably used from the viewpoints of easy availability, handling, and reactivity.

（式（３）中、Ｒ_１は１価の炭化水素基（脂肪族または芳香族）を表し、好ましくは炭素数が１〜２５、より好ましくは２〜２５、さらに好ましくは２〜１８の１価の脂肪族炭化水素基（好ましくはアルキル基）、または炭素数６から２０の芳香族環を含む１価の炭化水素基を表し；Ｒ_２は、アルコール性水酸基と結合した基であって、それぞれ独立して、２価の炭化水素基を表し、好ましくは炭素数が１〜２５、より好ましくは２〜２５、さらに好ましくは２〜１８、特に好ましくは２〜６の２価の脂肪族炭化水素基（好ましくはアルキレン基）、または炭素数６から２０の芳香族環を含む２価の炭化水素基を表し、前記炭化水素基はいずれもその構造中に環状構造を有してもよく、またＮ、Ｓ、Ｏなどのヘテロ原子を有してもよい。

(In the formula (3), R ₁ represents a monovalent hydrocarbon group (aliphatic or aromatic), preferably 1 to 25 carbon atoms, more preferably 2 to 25 carbon atoms, still more preferably 1 to 2-18 carbon atoms. A monovalent hydrocarbon group (preferably an alkyl group) or a monovalent hydrocarbon group containing an aromatic ring having 6 to 20 carbon atoms; R ₂ is a group bonded to an alcoholic hydroxyl group; Each independently represents a divalent hydrocarbon group, preferably a divalent aliphatic carbon having 1 to 25 carbon atoms, more preferably 2 to 25 carbon atoms, still more preferably 2 to 18 carbon atoms, particularly preferably 2 to 6 carbon atoms. Represents a hydrogen group (preferably an alkylene group) or a divalent hydrocarbon group containing an aromatic ring having 6 to 20 carbon atoms, and all of the hydrocarbon groups may have a cyclic structure in the structure; Moreover, you may have hetero atoms, such as N, S, and O.

  Preferable examples of the phosphine compound represented by the general formula (3) include n-butyl-bis (3-hydroxypropyl) phosphine oxide, n-propyl-bis (3-hydroxypropyl) phosphine oxide, and ethyl-bis. (3-hydroxypropyl) phosphine oxide, methyl-bis (3-hydroxypropyl) phosphine oxide, phenyl-bis (3-hydroxypropyl) phosphine oxide, ethyl-bis (2-hydroxyethyl) phosphine oxide, methyl-bis (2 -Hydroxyethyl) phosphine oxide, phenyl-bis (2-hydroxyethyl) phosphine oxide, methyl-bis (hydroxymethyl) phosphine oxide, phenyl-bis (hydroxymethyl) phosphine oxide and the like.

  In addition, n-butyl-bis (3-hydroxypropyl) phosphine oxide is preferable because a commercial product can be obtained as PO-4500 manufactured by Nippon Chemical Industry Co., Ltd.

（式（４）中、各Ｒ_３は、それぞれ独立して炭素数が１から２０の１価の炭化水素（好ましくは炭素数が１から１８特に炭素数が１から６の１価の脂肪族炭化水素基、または炭素数６から２０の芳香族環を含む１価の炭化水素基）を表し、これらは基中にエーテル結合またはエステル結合を有することができ、また水酸基を含有していてもよい。各Ｒ_４は、それぞれ独立して炭素数が１から２０の２価の炭化水素基（好ましくは炭素数が１から１８特に炭素数が１から６の２価の脂肪族炭化水素基、または炭素数６から２０の芳香族環を含む２価の炭化水素基）を表し、これらは基中にエーテル結合またはエステル結合を有することができ、また水酸基を含有していてもよい。）

(In Formula (4), each R ₃ is independently a monovalent hydrocarbon having 1 to 20 carbon atoms (preferably a monovalent aliphatic having 1 to 18 carbon atoms, particularly 1 to 6 carbon atoms). Represents a hydrocarbon group or a monovalent hydrocarbon group containing an aromatic ring having 6 to 20 carbon atoms), and these groups may have an ether bond or an ester bond, and may contain a hydroxyl group. Each R ₄ is independently a divalent hydrocarbon group having 1 to 20 carbon atoms (preferably a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 6 carbon atoms, Or a divalent hydrocarbon group containing an aromatic ring having 6 to 20 carbon atoms), which can have an ether bond or an ester bond in the group, and may contain a hydroxyl group.

  Specific examples of the aminophosphonate polyol represented by the general formula (4) include diisopropyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, diisobutyl-N, N-bis (2-hydroxyethyl) amino. Methylphosphonate, dioctyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, dioctadecyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, diethyl-N, N-bis (2-hydroxyethyl) ) Aminomethylphosphonate, diethyl-N, N-bis (2-hydroxypropyl) aminomethylphosphonate and the like. Among them, preferred examples include diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate commercially available as “ADEKA POLYOL FC-450” from ADEKA Corporation.

（式（５）中、各Ｒ_５及びＲ_６はそれぞれ独立に炭素数が１から２０の２価の炭化水素基（好ましくは炭素数が１から１８特に炭素数が１から６の２価の脂肪族炭化水素基、または炭素数６から２０の芳香族環を含む２価の炭化水素基）を表し、各Ｒ_７はそれぞれ独立に炭素数が１から１８特に炭素数が１から６の１価の脂肪族炭化水素基、または炭素数６から２０の芳香族環を含む１価の炭化水素基を表し、前記炭化水素基はいずれもその構造中に環状構造を有してもよく、またＮ、Ｓ、Ｏなどのヘテロ原子を有してもよい。
ｍおよびｎは、少なくともいずれか一方が１以上であることを条件として、それぞれ独立に０から１０００の整数である。）

(In Formula (5), each R ₅ and R ₆ is independently a divalent hydrocarbon group having 1 to 20 carbon atoms (preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 6 carbon atoms). An aliphatic hydrocarbon group or a divalent hydrocarbon group containing an aromatic ring having 6 to 20 carbon atoms), and each R ₇ independently represents 1 to 18 carbon atoms, particularly 1 to 6 carbon atoms. Represents a monovalent aliphatic hydrocarbon group or a monovalent hydrocarbon group containing an aromatic ring having 6 to 20 carbon atoms, and any of the hydrocarbon groups may have a cyclic structure in the structure thereof; You may have hetero atoms, such as N, S, and O.
m and n are each independently an integer of 0 to 1000, provided that at least one of them is 1 or more. )

As a suitable example, the trade name “EXOLIT” of Clariant Japan Co., Ltd.
Examples thereof include water-soluble hydroxy group-containing oligomeric phosphorus polyols commercially available as “OP550” and the like. This material can be prepared, for example, from a reaction product in a 2: 2: 8: 1 molar ratio of dimethylmethylphosphonate, phosphorus pentoxide, ethylene oxide and water.

  Moreover, as the phosphorus compound A (OH) n having 3 or 4 or more alcoholic hydroxyl groups, for example, in the above formulas (3) to (5), a hydrocarbon group to which OH is not bonded has an OH group. Or a compound in which the hydrocarbon group to which OH is bonded in the above formulas (3) to (5) further has an OH group.

Examples of the phosphorus compound A (OH) n having three alcoholic hydroxyl groups include compounds in which, in the above formula (3), R ¹ has an OH group or one of R ² further has an OH group. it can. Examples of the compound in which R ¹ has OH include 4-hydroxybutyl-bis (3-hydroxypropyl) phosphine oxide, tris (3-hydroxypropyl) phosphine oxide, 2-hydroxyethyl-bis (3-hydroxypropyl). ) Phosphine oxide, hydroxymethyl-bis (3-hydroxypropyl) phosphine oxide, tris (2-hydroxyethyl) phosphine oxide, hydroxymethyl-bis (2-hydroxyethyl) phosphine oxide, tris (hydroxymethyl) phosphine oxide, etc. be able to.

  In one embodiment of the present invention, the following formula (6) can be used as the phosphorus-containing polycarbonate polyol. The polycarbonate diol containing a phosphorus atom in the molecule preferably has a number average molecular weight of about 500 to 10,000. Moreover, m / (m + n) is preferably 0.01 to 1.0.

（式中、Ａ^１およびＢは、前述の意味を有し、ｍは正の整数を表し、ｎはゼロ又は正の整数を表す。）
なお、一般式（６）において、ｍ及びｎは、分子内で括弧内の繰返し単位がどのような割合で存在するかを示すものであって、前記繰返し単位がブロック化したことを限定的に意味するものではない。また、通常ｍは１〜１００であり、ｎは０〜１００である。

(Wherein A ¹ and B have the above-mentioned meanings, m represents a positive integer, and n represents zero or a positive integer.)
In the general formula (6), m and n indicate the ratio of the repeating units in parentheses in the molecule, and the fact that the repeating units are blocked is limited. It doesn't mean. Moreover, normally m is 1-100 and n is 0-100.

The method for preparing the phosphorus-containing polycarbonate polyol used in the present invention will be described below.
[First method]
The polycarbonate polyol is subjected to a transesterification reaction with the phosphorus compound A (OH) n (particularly preferably n = 2, and the same applies to the following description in this method). In this reaction, if necessary, a divalent alcohol compound may be further added to the reaction.

  The polycarbonate polyol is preferably a polycarbonate diol represented by the formula (7). However, in Formula (7), R represents a C2-C25 (preferably 2-15) alkylene group, k represents the integer of 1-150. As this polycarbonate diol, any known method may be used. For example, transesterification of a dihydric alcohol (HO—R—OH) having an alkylene group having 4 to 25 carbon atoms (preferably 4 to 15 carbon atoms) corresponding to R in Formula (7) with a carbonate compound, carbon number 2 To 25 (preferably 2 to 15) of a cyclic carbonate having an alkylene group, or a product produced by a reaction of the aliphatic dihydric alcohol with a chloroformate or phosgene can be used. . In these, the polycarbonate diol manufactured by transesterification with the dihydric alcohol which has the said C4-C25 (preferably 4-15) alkylene group and a carbonate compound is preferable. Examples of the carbonate compound include aliphatic or aromatic carbonates (carbonate esters) such as dialkyl carbonate, diaryl carbonate, alkylene carbonate, and alkylaryl carbonate. Specific examples include dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, diphenyl carbonate, methylphenyl carbonate, ethylene carbonate, propylene carbonate, and the like. Copolymer polycarbonates in which two or more dihydric alcohols having an alkylene group are used in combination can also be used.

（式（７）中、ｋは１から１５０の整数である。）

(In formula (7), k is an integer from 1 to 150.)

  This polycarbonate polyol may be a commercially available product. Preferable examples of this polycarbonate polyol include ETERNACOLL (registered trademark) series manufactured by Ube Industries, Ltd., Kuraray polyol series manufactured by Kuraray Co., Ltd., and PACCEL (registered trademark) series manufactured by Daicel Chemical Industries. These polycarbonate polyols can be used alone or in combination of two or more. Further, the number average molecular weight of these polycarbonate polyols is preferably 500 or more, more preferably 2000 to 20000. When the number average molecular weight of the polycarbonate polyol is small, the molecular weight of the phosphorus-containing polycarbonate polyol to be produced is lowered. On the other hand, when the number average molecular weight is large, the viscosity is high and handling becomes difficult.

  As the phosphorus compound A (OH) n to be reacted, the above-mentioned (3) to (5) are preferably mentioned.

  The first method is, for example, a method in which polycarbonate polyol and phosphorus compound A (OH) n are charged and reacted at a predetermined ratio, or a molten polycarbonate polyol and phosphorus compound A (OH) n are continuously mixed at a predetermined ratio. The reaction can be carried out batchwise or continuously depending on the method of supplying to the reaction.

  The charging ratio for the transesterification reaction of the phosphorus compound A (OH) n and the polycarbonate polyol is 0.001 to 10 mol, preferably 0.01 to 1 mol, of the polycarbonate polyol with respect to 1 mol of the phosphorus compound A (OH) n. Most preferably, it is 0.05-0.5 mol. When the charging ratio of the polycarbonate polyol is small, the molecular weight of the produced phosphorus-containing polycarbonate polyol is lowered. On the other hand, when the charging ratio is high, the phosphorus content of the phosphorus-containing polycarbonate polyol is lowered.

  The reaction temperature is preferably 50 to 300 ° C, preferably 50 to 250 ° C, more preferably 100 to 180 ° C. The reaction pressure is not particularly limited. For example, the reaction is carried out at normal pressure. The reaction atmosphere is usually an inert gas atmosphere such as nitrogen, argon or helium.

  In the first method, it is preferable to use a transesterification catalyst as necessary. If the polycarbonate polyol is obtained by reacting a carbonate compound and the corresponding diol, and the transesterification catalyst remains active in the polycarbonate polyol, it is allowed to react without adding the transesterification catalyst. However, in other cases, it is preferable to newly add a transesterification catalyst for reaction. The amount of the transesterification catalyst used is preferably 1 to 5000 ppm, more preferably 10 to 1000 ppm on a weight basis with respect to the total amount charged.

  The transesterification catalyst is not particularly limited as long as it is a compound that catalyzes the transesterification reaction. For example, titanium compounds such as titanium tetrachloride and tetraalkoxy titanium (tetra-n-butoxy titanium, tetraisopropoxy titanium, etc.), metal tin, tin hydroxide, tin chloride, dibutyltin laurate, dibutyltin oxide, butyltin A tin compound such as tris (ethylhexanoate) is preferred. Among these, tetraalkoxytitanium (tetra-n-butoxytitanium, tetraisopropoxytitanium, etc.), dibutyltin laurate, dibutyltin oxide, and butyltin tris (ethylhexanoate) are preferable. Tetra-n-butoxy titanium, tetraisopropoxy titanium, etc.) are particularly preferred.

  In the phosphorus-containing polycarbonate polyol produced by the first method, a divalent residue derived from the polycarbonate polyol used as a raw material for the reaction, for example, a polycarbonate diol of the above formula (7) is used as the residue B. Includes the group -R-. In addition, when a divalent alcohol compound is added to the reaction, a residue obtained by removing two OH from the alcohol compound is further included.

[Second method]
Phosphorus compound A (OH) n (particularly preferably n = 2, and this method is the same in the following description) is reacted with a carbonate compound or phosgene. In this reaction, if necessary, a divalent alcohol compound may be further added to the reaction.

  The charging ratio is preferably 0.5 to 1 mol of the carbonate compound or phosgene with respect to 1 mol of the polyol component (total of the phosphorus compound A (OH) n and further added divalent alcohol).

  Examples of the carbonate compound to be used include aliphatic or aromatic carbonates (carbonates) such as dialkyl carbonate, diaryl carbonate, alkylene carbonate, and alkylaryl carbonate. Specific examples include dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, diphenyl carbonate, methylphenyl carbonate, ethylene carbonate, propylene carbonate, and the like.

  This reaction is a transesterification reaction and can be carried out according to a known transesterification method for producing a polycarbonate polyol. That is, in the presence of a transesterification catalyst, if necessary, by carrying out a transesterification reaction while continuously extracting an aliphatic or aromatic compound having a by-produced hydroxyl group out of the reaction system, the phosphorus-containing compound used in the present invention A polycarbonate polyol can be suitably prepared.

  The transesterification catalyst is not particularly limited as long as it is a compound that catalyzes the transesterification reaction. For example, titanium compounds such as titanium tetrachloride and tetraalkoxy titanium (tetra-n-butoxy titanium, tetraisopropoxy titanium, etc.), metal tin, tin hydroxide, tin chloride, dibutyltin laurate, dibutyltin oxide, butyltin A tin compound such as tris (ethylhexanoate) is preferred. Among these, tetraalkoxytitanium (tetra-n-butoxytitanium, tetraisopropoxytitanium, etc.), dibutyltin laurate, dibutyltin oxide, and butyltin tris (ethylhexanoate) are preferable. Tetra-n-butoxy titanium, tetraisopropoxy titanium, etc.) are particularly preferred. When the transesterification catalyst is used, the amount used is preferably 1 to 5000 ppm, more preferably 10 to 1000 ppm, based on the weight of the polyol.

  The conditions for the transesterification reaction are not particularly limited as long as the target product can be produced, but at 80 to 250 ° C. (especially 110 to 200 ° C.) under normal pressure so that the target product can be produced efficiently. About 1 to 24 hours, then react under reduced pressure at 80 to 250 ° C. (especially 110 to 240 ° C.) for about 0.1 to 20 hours, and further gradually increase the degree of vacuum at the same temperature to finally become 20 mmHg or less. The reaction is preferably carried out under reduced pressure for about 0.1 to 20 hours. In order to extract by-product phenol and by-product alcohol, it is preferable to provide a distillation column in the reactor, and the reaction may be carried out under the flow of an inert gas (nitrogen, helium, argon, etc.).

  In the second method, when a divalent alcohol compound is added to the reaction, a residue obtained by removing two OHs from the alcohol compound is included as a residue B in the resulting phosphorus-containing polycarbonate polyol. When a divalent alcohol compound is not added to the reaction, the phosphorus-containing polycarbonate polyol does not contain the residue B, and the phosphorus-containing structural unit represented by the structural unit (I) of the carbonate structural unit and the residue A ( II).

  The second method has an advantage that the structural unit (II) represented by the residue A can be controlled relatively freely from a low ratio to a high ratio, and as a result, it can be manufactured from a product having a low phosphorus content to a high product. .

  As described in the above [First method] and [Second method], in each reaction, a divalent alcohol compound is added to the reaction as necessary to obtain a residue derived from the dihydric alcohol compound. Can be introduced as residue B into the phosphorus-containing polycarbonate polyol used in the present invention.

  Examples of the divalent alcohol compound include 2-methyl-1,3-propanediol, 1,3-butanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, 2-methyl- 2-propyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2- Compounds in which an alkylene group such as butyl-2-ethyl-1,3-propanediol is a trimethylene group; Compounds in which an alkylene group such as 1,4-butanediol is a tetramethylene group; 1,5-pentanediol, 3- Compounds in which the alkylene group is a pentamethylene group such as methyl-1,5-pentanediol and 1,5-hexanediol; 1,6-hexanediol Compounds in which an alkylene group such as 2-ethyl-1,6-hexanediol is a hexamethylene group; Compounds in which an alkylene group such as 1,7-heptanediol is a heptamethylene group; 1,8-octanediol, 2-methyl Compounds in which the alkylene group of -1,8-octanediol is an octamethylene group; 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,20- Compounds having a long-chain alkylene group such as eicosanediol; 1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexane-1,4-dimethanol, cyclohexane-1,4-diethanol, 2,2-bis ( 4-hydroxycyclohexyl) propane, 2,7-norbornanediol, 1,4 Compounds in which an alkylene group such as benzenedimethanol has a substituent or a part of the alkylene group forms a ring (an alicyclic ring and an aromatic ring); diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene Compounds in which some of the carbon atoms in the alkylene group such as glycol and polytetramethylene glycol are substituted with oxygen, sulfur and nitrogen atoms; 2,5-tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane A part of the carbon atoms in the alkylene group such as oxygen, sulfur, and nitrogen atoms are substituted, and the alkylene group has a substituent or part of the alkylene group is a ring (alicyclic ring and aromatic ring). Examples of the compound are formed.

  The phosphorus-containing polycarbonate polyol preferably has a number average molecular weight of about 500 to 10,000, preferably about 500 to 5,000, and more preferably about 500 to 3,000. For this reason, when the hydroxyl value (molecular weight) of the reaction product is outside the target range, that is, when the molecular weight is small, the reaction is performed while distilling further diol under reduced pressure, and when the molecular weight is large, the diol is added and further It is preferable to adjust the molecular weight by a known method such as transesterification. If necessary, it is preferable to deactivate the remaining transesterification catalyst with water or a phosphorus compound (phosphoric acid, butyl phosphate, dibutyl phosphate, etc.) after adjusting the molecular weight.

  This manufacturing method has been filed as a patent application as PCT / JP2008 / 62191 by the present inventors.

  According to the above method for producing a phosphorus-containing polycarbonate polyol (preferably polycarbonate diol), substantially all the raw material phosphorus compound A (OH) n can be transesterified and introduced into the polycarbonate polyol molecule. Here, “substantially all” means 90% or more, preferably 95% or more, more preferably 98% or more. This point can be easily confirmed by the fact that the peak of the phosphorus compound A (OH) n substantially disappears by GPC analysis of the reaction mixture.

  Therefore, in this production method, when “substantially all” the phosphorus compound A (OH) n as a raw material is subjected to a transesterification reaction, the reaction mixture should be used as it is as a raw material for producing the polyurethaneimide resin of the present invention. Is preferred.

  On the other hand, the hard segment in the polyurethane resin of the present invention preferably contains structural units represented by the following formulas (H1) to (H4).

（式中、Ｄは直接結合、−Ｏ−、−ＣＨ_２−、−ＣＯ−、−ＳＯ_２−のいずれかを表す。）

(In the formula, D represents any of a direct bond, —O—, —CH ₂ —, —CO—, and —SO ₂ —).

  As shown below, these structural units are derived from a tri- or higher functional polycarboxylic acid or a derivative thereof and introduced into the molecule.

  The method for synthesizing the polyurethaneimide resin of the present invention is not limited, but can be easily obtained by the conventionally known method (i) or (ii) as described above.

  The method (i) is a production method in which at least 1) a phosphorus-containing polycarbonate polyol, 2) a polyvalent isocyanate compound, 3a) a tri- or higher functional polycarboxylic acid or a derivative thereof is reacted in a solvent. After reacting the phosphorus-containing polycarbonate polyol and the polyvalent isocyanate compound at 20 to 150 ° C., preferably 60 to 120 ° C. for 0.1 to 12 hours, a tri- or higher functional polycarboxylic acid or derivative thereof is added, and 80 to 250 ° C. The reaction can be preferably carried out at 120 to 200 ° C. for 0.5 to 24 hours. In this reaction, a catalyst such as an acid or a base can be used.

  The method (ii) is a production method in which at least 1) a phosphorus-containing polycarbonate polyol, 2) a polyvalent isocyanate compound, and 3b) a polyol composed of an imide bond are reacted in a solvent. In this reaction, a diol component such as a phosphorus-containing polycarbonate polyol or a polyol containing an imide bond and a polyvalent isocyanate compound are reacted at 20 to 150 ° C., preferably 60 to 120 ° C. for 0.1 to 12 hours. It is also possible to obtain a prepolymer by reacting a phosphorus-containing polycarbonate polyol and a polyvalent isocyanate compound at 20 to 150 ° C., preferably 60 to 120 ° C. for 0.1 to 12 hours, and then including an imide bond. The obtained polyol is added, and the chain extension reaction can be carried out at 20 to 150 ° C., preferably 60 to 120 ° C. for 1 to 24 hours. In this reaction, a catalyst usually used for urethane reaction can also be used.

  The polyisocyanate used here is preferably a diisocyanate. As the diisocyanate compound, any compound may be used as long as it has two isocyanate groups in one molecule. For example, an aliphatic, alicyclic or aromatic diisocyanate, preferably an aliphatic, alicyclic or aromatic diisocyanate having 2 to 30 carbon atoms excluding an isocyanate group, specifically 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexame Thiylene diisocyanate, lysine diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis (isocyanate methyl) ) -Cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphth Range diisocyanate - DOO, tolidine diisocyanate - DOO, xylylene diisocyanate - DOO etc. can be preferably exemplified. The diisocyanate compound of the present invention may be a blocked diisocyanate in which an isocyanate group is blocked with a blocking agent.

  In addition, as the trifunctional or higher polycarboxylic acid or derivative thereof used in the method (i), aromatic tricarboxylic acid, aromatic tetracarboxylic acid, and derivatives thereof have good heat resistance and mechanical properties. At the same time, the effect of improving the combustion resistance is excellent, which is preferable. Specifically, trimellitic anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-benzenedicarboxylic acid anhydride) hexafluoropropane, pyromellitic dianhydride, 1,4-bis (3,4-benzenedicarboxylic anhydride) benzene, 2,2-bis [4- (3,4-phenoxydicarboxylic anhydride) phenyl] propane, 2,3,6,7-naphthalene Tetracarboxylic Dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride , Aromatic polycarboxylic anhydrides such as aromatic tetracarboxylic dianhydrides such as 1,1-bis (2,3-dicarboxyphenyl) ethane, and cyclopentanetetracarboxylic dianhydrides, 1,2 Preferred examples include alicyclic tetracarboxylic anhydrides such as 1,4,5-cyclohexanetetracarboxylic dianhydride and 3-methyl-4-cyclohexene-1,2,4,5-tetracarboxylic dianhydride. be able to. Among these, in particular 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, and 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride and trimellitic anhydride are suitable because the resulting polyurethaneimide resin has excellent solubility in organic solvents.

  Moreover, if the polyol comprised by including the imide bond used by the method of (ii) has two or more hydroxyl groups which react with an isocyanate group at the terminal and has at least an imide bond in the molecule, Although not limited, for example, a bifunctional hydroxyl-terminated imide oligomer represented by the following general formula (H5) can be suitably used. In addition, although this bifunctional hydroxyl-terminated imide oligomer is not limited, it can be easily obtained by a known method. Patent Document 4 has a detailed description.

（式中、Ｘはテトラカルボン酸のカルボキシル基を除いた残基を表し、Ｙはジアミンのアミノ基を除いた残基を表し、Ｚは２価の脂肪族又は芳香族炭化水素基を表し、ｎはポリイミド構造の繰り返し数であり、０〜２０の整数を表す。）

(In the formula, X represents a residue obtained by removing a carboxyl group of tetracarboxylic acid, Y represents a residue obtained by removing an amino group of diamine, Z represents a divalent aliphatic or aromatic hydrocarbon group, n is the number of repetitions of the polyimide structure, and represents an integer of 0 to 20.)

  In the polyurethaneimide resin of the present invention, the soft segment is a segment formed from a phosphorus-containing polycarbonate polyol (preferably polycarbonate diol), and the hard segment is a polyisocyanate compound and a polycarboxylic acid having three or more functions. Alternatively, it is a segment formed from a derivative thereof or a segment formed from a polyol composed of a polyisocyanate compound and an imide bond.

  A typical example of the polyurethaneimide resin produced by the method (i) has the following structure.

ここで、Ｅは、リン含有ポリカーボネートポリオールに由来する残基Ａ、残基Ａ^１、残基Ｂ等を表し、Ｇは、ジイソシアネート化合物から２つのイソシアネート基を除いた残基を表し、Ｘは、テトラカルボン酸のカルボキシル基を除いた残基を表す。ｍはポリカーボネートポリオール構造の繰り返し数を表す。また、鍵括弧［ ］で囲まれた部分は、繰り返し単位を意味する。

Here, E represents a residue A, a residue A ¹ , a residue B or the like derived from a phosphorus-containing polycarbonate polyol, G represents a residue obtained by removing two isocyanate groups from a diisocyanate compound, and X represents Represents a residue excluding the carboxyl group of tetracarboxylic acid. m represents the repeating number of the polycarbonate polyol structure. The part enclosed in square brackets [] means a repeating unit.

  A typical example of the polyurethaneimide resin produced by the method (ii) has the following structure.

ここで、Ｅは、リン含有ポリカーボネートポリオールに由来する残基Ａ、残基Ａ^１、残基Ｂ等を表し、Ｇは、ジイソシアネート化合物から２つのイソシアネート基を除いた残基を表し、Ｘはテトラカルボン酸のカルボキシル基を除いた残基、Ｙはジアミンのアミノ基を除いた残基を表し、Ｚは２価の脂肪族又は芳香族炭化水素基を表す。ｍはポリカーボネートポリオール構造の繰り返し数を表す。ｎはポリイミド構造の繰り返し数であり、０〜２０の整数を表す。また、鍵括弧［ ］で囲まれた部分は、それぞれ繰り返し単位を意味し、２つの繰り返し単位は、ランダムに結合されていてもよく、ブロック化して結合されていてもよい。

Here, E represents a residue A, a residue A ¹ , a residue B or the like derived from a phosphorus-containing polycarbonate polyol, G represents a residue obtained by removing two isocyanate groups from a diisocyanate compound, and X represents a tetra The residue except the carboxyl group of carboxylic acid, Y represents the residue except the amino group of diamine, Z represents a bivalent aliphatic or aromatic hydrocarbon group. m represents the repeating number of the polycarbonate polyol structure. n is the number of repetitions of the polyimide structure and represents an integer of 0-20. Moreover, the part enclosed by bracket | parenthesis [] means a repeating unit, respectively, and two repeating units may be couple | bonded at random or may be block-coupled.

  The two structural formulas shown here are examples shown for understanding the reactions (i) and (ii), and are not limited thereto.

  The polyurethane imide resin of the present invention is 100% by weight as a whole, and the soft segment is 10 to 90% by weight, preferably 20 to 80% by weight, and the hard segment is 90 to 10% by weight, preferably 80 to 20% by weight. preferable. This ratio can be easily controlled by the ratio of the raw material components.

  The phosphorus content of the polyurethaneimide resin of the present invention (phosphorus atom weight% in the polyurethaneimide resin) is 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more. It is preferable to improve the flame resistance. The upper limit of the phosphorus content is naturally determined by the composition such as the proportion of the hard segment, but is usually 30% by weight or less, particularly 20% by weight or less.

  The phosphorus content of the polyurethaneimide resin can be easily controlled by using a phosphorus-containing polycarbonate polyol having a known phosphorus content as a raw material component. A phosphorus-containing polycarbonate polyol having a known phosphorus content can be easily obtained by making the raw material components at a ratio that makes the target phosphorus content in advance and reacting them "substantially all" when producing the polycarbonate polyol. Can do. Whether or not “substantially all” transesterification has occurred can be confirmed by GPC measurement of the reaction mixture.

  You may introduce | transduce into the polyurethane imide resin of this invention the segment which has a reactive group which can react with an epoxy group, an isocyanate group, etc. further. By setting it as the polyurethane imide resin which has such a reactive group, when a resin composition is formed combining with an epoxy compound, an isocyanate compound, etc., a hardened | cured material can be suitably obtained from the said resin composition.

  The introduction of a segment having a reactive group is not limited. For example, a diol compound having a thermal reactive group such as a carboxy group or a phenolic hydroxyl group or a photoreactive group such as a methacrylic group is used as the above 1) to 3a). Or it can carry out easily by making it react with the compound of 1) -3b).

  Specific examples of the diol compound having a reactive group include 2,2-bis (hydroxymethyl) propionic acid and 2,2-bis (hydroxymethyl) butyric acid as diol compounds having a carboxyl group. Can do. Examples of the diol compound having a phenolic hydroxyl group include 2,6-bis (hydroxymethyl) -phenol and 2,6-bis (hydroxymethyl) -p-cresol.

  The polyurethane imide resin of the present invention is obtained by combining a resin composition with another resin component such as an epoxy compound or a polyisocyanate compound in an organic solvent, a filler component such as an inorganic filler, and a curing catalyst as necessary. It can be suitably obtained. A cured film can be suitably obtained by forming a coating film on the surface of the substrate by, for example, printing this resin composition, and then drying and curing the coating film by a conventionally known method such as heating or light irradiation. . This cured film preferably has various properties such as flexibility, heat resistance, low warpage, electrical insulation, printability, solder resistance, solvent resistance and mechanical strength required as an insulating protective film for flexible substrates. It is a cured film with improved combustion resistance without degrading properties.

  Hereinafter, the present invention will be described in detail by way of examples. In addition, this invention is not limited to a following example.

In the following examples, measurement and evaluation were performed by the following methods.
[Solution viscosity]
Measurement was performed at a temperature of 25 ° C. and a rotation speed of 10 rpm using a viscometer TV-20 manufactured by Toki Sangyo Co., Ltd.

[Initial elastic modulus, elongation, breaking strength]
The sample solution was applied to a glass plate whose surface was peeled off, and heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 60 minutes to obtain a sheet-like sample having a thickness of about 100 μm. This sheet-like sample was cut into a width of 1 cm and a length of 7 cm and used as a test piece. Measured using a tensile tester (Orientec; Tensilon UCT-5T) at a temperature of 25 ° C., a humidity of 50% RH, a crosshead speed of 50 mm / min, and a distance between chucks of 5 cm. The breaking strength was determined.

[Volume resistance, surface resistance]
The sample solution was applied to a glass plate whose surface was peeled off, and heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 60 minutes to obtain a sheet-like sample having a thickness of about 100 μm. This sheet-like sample was measured according to JIS C2103 as a test piece.

[Oxygen index]
The sample solution was applied to a glass plate whose surface was peeled off, and heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 60 minutes to obtain a sheet-like sample having a thickness of about 100 μm. Using this sheet-like sample as a test piece, JIS
It measured based on K7201-2. However, since the sheet-like sample of the present invention is flexible and not self-supporting, measurement was performed by fixing the sample to a metal frame having a width of 38 mm and a height of 120 mm.

[Low warpage]
The resin composition of the sample is applied to the surface of a polyimide film (UPILEX 35SGA) manufactured by Ube Industries, Ltd. to form a coating film, and heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 60 minutes to form a 10 μm thick cured film. Formed. The obtained polyimide film and cured film laminate is cut into a 5 cm × 5 cm square to form a test piece, which is placed on a horizontal surface with the cured film on the top, and from the four horizontal corners of the test piece. The height of was measured. The average value of the heights of the four corners from the horizontal plane was determined as an index of warpage.

[Bendability]
The resin composition of the sample is applied to the surface of a polyimide film (UPILEX 35SGA) manufactured by Ube Industries, Ltd. to form a coating film, and heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 60 minutes to form a 10 μm thick cured film. Formed. The obtained polyimide film and cured film laminate was cut into a 2 cm long x 1 cm wide rectangle to obtain a test piece. The test piece was folded so that the cured film was inward in the center in the length direction, and a 500 g weight was placed on the bent portion and allowed to stand for 1 minute. After removing the weight, the bent part of the test piece was observed with a microscope, and the case where there was no abnormality was indicated as ◯, and the case where cracks, whitening, etc. were observed was indicated as x.

[Flame Retardancy (UL94V-0)]
The resin composition of the sample is applied to the surface of a polyimide film (UPILEX 35SGA) manufactured by Ube Industries, Ltd. to form a coating film, and heat-treated at 80 ° C. for 30 minutes and then at 120 ° C. for 60 minutes to form a 10 μm thick cured film. Formed. The obtained laminate of polyimide film and cured film was cut into a rectangle of 5 inches × 0.5 inches to obtain a test piece.

Evaluation of flame resistance was performed according to the UL94 standard vertical combustion test method. That is, the test piece was held on a stand with a clamp in the vertical direction, and the upper portion was fixed with a clamp so that the lower end thereof was 12 inches (304.8 mm) in height. Absorbent cotton was placed under the sample to confirm ignition when a fireball fell. A burner adjusted to a flame of 0.75 inch (19.05 mm) at the center of the lower end of the test piece was indirect flame for 10 seconds (the portion at the bottom of the sample 1 inch (25.4 mm)), the flame was released, and the burning time of the sample was measured. Immediately after extinguishing the fire, the indirect flame was again applied for 10 seconds, and the combustion (red heat) time was measured. In the measurement, n = 5 was set as one set, and two sets were tested (10 points in total). The following items were confirmed as criteria for UL94V-0. Those that satisfy all of these items are acceptable.
(1) Does not continue to burn for more than 10 seconds after the first flame contact (2) Burning time after flame contact of 5 points x 2 times (10 times in total) within 50 seconds (3) 12 inches down by fireball dripping (4) Red hot burning time after the second flame contact is within 30 seconds (5) Does not burn up to the clamp part

[Solid content]
The sample solution was placed in an aluminum petri dish with a weight W1 (g), dried by heating at 150 ° C. for 4 hours, and then the weight W2 (g) of the dried sample was measured. The solid content concentration was determined from X (%) = W1 / W2 × 100.

[Hydroxyl value]
It carried out according to JIS-K-1557.

[Reaction rate of phosphorus compound (GPC measurement)]
Using a LC-10 (GPC column KF-80M × 2, KF-802) manufactured by Shimadzu Corporation, measurement was performed using THF as a solvent, and a number average molecular weight was determined using a polystyrene standard sample.

The compounds used in the following examples are as follows.
[Phosphorus compounds]
Hishicolin PO-4500 (Nippon Chemical Industry Co., Ltd., n-butyl-bis (3-hydroxypropyl) phosphine oxide)
[Polycarbonate diol]
Kuraray polyol C-5090 (manufactured by Kuraray Co., Ltd., hydroxyl value 22.6 mgKOH / g)
ETERNACOLL UH-CARB100N (manufactured by Ube Industries, Ltd., hydroxyl value 110 mgKOH / g)
[Transesterification catalyst]
Tetra-n-butoxy titanium (manufactured by Wako Pure Chemical Industries, Ltd.)
[Catalyst deactivator]
Di-n-butyl phosphite (Wako Pure Chemical Industries, Ltd.)
[Polycarboxylic acid derivatives]
2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (manufactured by Ube Industries, Ltd.)
Trimellitic anhydride (Wako Pure Chemical Industries, Ltd.)
[Diamine compound]
Isophoronediamine (manufactured by Wako Pure Chemical Industries, Ltd.)
[Monoamine having one alcoholic hydroxyl group]
3-Aminopropanol (Wako Pure Chemical Industries, Ltd.)
[Chain extender]
2,2-bis (hydroxymethyl) propionic acid (manufactured by Guangei Perstorp)
[Polyisocyanate compound]
Coronate T-80 (Nippon Polyurethane Industry Co., Ltd.)
[Organic solvent]
γ-Butyrolactone (Wako Pure Chemical Industries, Ltd.)
Ethanol (made by Wako Pure Chemical Industries, Ltd.)
[Epoxy compound]
Epicote 828EL (Japan Epoxy Resin Co., Ltd., epoxy equivalent: 184-194)
[Curing catalyst]
Cureazole 2E4MZ (manufactured by Shikoku Chemicals Co., Ltd., 2-ethyl-4-methylimidazole)
[Filler]
Aerosil R972 (Nippon Aerosil Co., Ltd., specific surface area (BET method): 110 m ² / g)

[Reference Example 1]
[Production of phosphorus-containing polycarbonate diol]
C-5090 150.00 g and PO-4500 53.55 g were added to a 300 mL glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, and dissolved by stirring at 100 ° C. for 1 hour. After raising the temperature to 160 ° C., 0.10 g of tetra-n-butoxytitanium was added and reacted with stirring for 8 hours. Next, the reaction mixture was cooled to 120 ° C., 0.13 g of di-n-butyl phosphite was added at 120 ° C., and the mixture was stirred for 2 hours to deactivate the catalyst.

  By this reaction, a phosphorus-containing polycarbonate diol having a viscosity of 16 Pa · s, a hydroxyl value of 150 mgKOH / g, and liquid at 20 ° C. was obtained. It was confirmed by GPC measurement that 98% or more of the raw material PO-4500 had reacted.

[Reference Example 2]
[Production of alcoholic hydroxyl-terminated imide oligomer solution]
In a 5 L glass separable flask equipped with a nitrogen introduction tube, a Dean-Star cleaver, and a cooling tube, 1471 g of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 507 g of ethanol, and 2092 g of γ-butyrolactone were added. The reaction was stirred and stirred at 90 ° C. for 1 hour under a nitrogen atmosphere. Next, 376 g of 3-aminopropanol and 426 g of isophoronediamine were charged into the reaction mixture, and the water produced by the imidization reaction was charged with nitrogen in the reaction solution while heating at 120 ° C. for 2 hours and 180 ° C. for 2 hours. It was removed by distributing.

  By the above reaction, an alcoholic hydroxyl group-terminated imide oligomer solution having a solid content concentration of 50% was obtained.

[Example 1]
[Production of polyurethane imide (1)]
A 300 mL glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube was charged with 37.50 g of the phosphorus-containing polycarbonate diol obtained in Reference Example 1, 13.20 g of Coronate T-80, and 50.69 g of γ-butyrolactone. The reaction was stirred at 80 ° C. for 2 hours. To this reaction mixture, 7.36 g of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 7.36 g of γ-butyrolactone were added, and the temperature was raised to 160 ° C., followed by stirring for 4 hours. It was.

  After completion of the reaction, 11.82 g of γ-butyrolactone was added to obtain a solution of polyurethaneimide (1) having a solid content concentration of 46 wt%, a viscosity of 89 Pa · s, and a phosphorus content of 2.35 wt%.

  Using this polyurethaneimide (1) solution, a sheet-like sample is prepared, and the mechanical properties (initial elastic modulus, elongation, breaking strength), electrical insulation (volume resistance, surface resistance), oxygen, of the polyurethaneimide (1) The index was measured. The results are shown in Table 1.

[Example 2]
[Production of polyurethane imide (2)]
A 300 mL glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube was charged with 37.50 g of the phosphorus-containing polycarbonate diol obtained in Reference Example 1, 13.21 g of Coronate T-80, and 50.69 g of γ-butyrolactone. The reaction was stirred at 80 ° C. for 2 hours. To this reaction mixture, 4.80 g of trimellitic anhydride and 4.80 g of γ-butyrolactone were added, and the temperature was raised to 160 ° C., followed by stirring for 4 hours for reaction.

  By this reaction, a solution of polyurethane imide (2) having a solid concentration of 50% by weight, a viscosity of 28.4 Pa · s, and a phosphorus content of 2.46% by weight was obtained.

  Table 1 shows the results of mechanical properties, electrical insulation, and oxygen index of polyurethaneimide (2) measured in the same manner as in Example 1.

Example 3
[Production of polyurethane imide (3)]
In a 300 mL glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 37.50 g of the phosphorus-containing polycarbonate diol obtained in Reference Example 1 and 10.40 g of the alcoholic hydroxyl group-terminated imide oligomer solution obtained in Reference Example 2 , 2,2-bis (hydroxymethyl) propionic acid 0.86 g, Coronate T-80 10.35 g, γ-butyrolactone 48.86 g were stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and then heated to 80 ° C. The mixture was reacted at a temperature of 4 hours with stirring.

  By this reaction, a solution of polyurethane imide (3) having a solid concentration of 50% by weight, a viscosity of 5.8 Pa · s, and a phosphorus content of 2.48% by weight was obtained.

  Table 1 shows the results of mechanical properties, electrical insulating properties, and oxygen index of polyurethaneimide (3) measured in the same manner as in Example 1.

[Comparative Example 1]
[Production of polyurethane imide (4) containing no phosphorus atom]
A 300 mL glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube is charged with 100.00 g of polycarbonate diol UH-CARB100N not containing phosphorus atoms, 35.22 g of coronate T-80, and 129.49 g of γ-butyrolactone. The reaction was stirred at 80 ° C. for 2 hours. To this reaction mixture, 29.44 g of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 29.44 g of γ-butyrolactone were added, and the temperature was raised to 160 ° C., followed by stirring for 4 hours. It was.

  By this reaction, a solution of polyurethane imide (4) containing 51 wt% solid content and having a viscosity of 2.6 Pa · s and containing no phosphorus was obtained.

  Table 1 shows the results of mechanical properties, electrical insulating properties, and oxygen index of polyurethaneimide (4) containing no phosphorus atom, measured in the same manner as in Example 1.

Example 4
[Production of Polyurethaneimide Resin Composition Containing Phosphorus Atom]
To the polyurethaneimide (1) solution obtained in Example 1, 5 parts by weight of epoxy resin 828EL and 0.5 part of curing catalyst 2E4MZ were added to 100 parts by weight of polyurethaneimide solids, and the mixture was uniformly stirred and mixed. Further, 7 parts by weight of Aerosil R972 as a filler was added and mixed, and then kneaded using three rolls to obtain a polyurethaneimide resin composition.

  The viscosity of this resin composition was measured with a rotational viscometer. Moreover, about the cured film which consists of this resin composition, about a mechanical characteristic (initial elastic modulus, elongation, breaking strength), curvature, bending, electrical insulation (volume resistance, surface resistance), and flame retardance (UL94V-0). It was measured. The results are shown in Table 2.

[Comparative Example 2]
[Production of polyurethaneimide resin composition containing no phosphorus atom]
A polyurethaneimide resin composition containing no phosphorus atom was obtained in the same manner as in Example 4 except that the polyurethaneimide (4) containing no phosphorus atom obtained in Comparative Example 1 was used.

  This resin composition was evaluated in the same manner as in Example 4. The results are shown in Table 2.

  From the above Examples and Comparative Examples, the polyurethane imide resin and the composition thereof of the present invention have excellent bendability, low warpage, and electrical insulation (volume resistance, surface resistance), while having an oxygen index and flame retardancy. As can be seen from the measurement results of the property (UL94V-0), it is clear that the flame resistance is improved.

According to the present invention, various properties such as flexibility, heat resistance, low warpage, electrical insulation, printability, solder resistance, solvent resistance, and mechanical strength required as an insulating protective film of a flexible substrate are provided. It is possible to provide a polyurethaneimide resin, a resin composition thereof, and a cured film having improved flame resistance without lowering.
As a result, since the flame resistance of the flexible substrate is improved, the safety of electronic devices such as a flat panel display, a mobile phone, and a personal computer using the flexible substrate can be greatly improved.

Claims (7)

In a polyurethaneimide resin comprising a soft segment made of polycarbonate polyol and a hard segment having an imide bond,
Polycarbonate polyol
Formula: -OCOO-
A structural unit (I) represented by:
Residue A
(However, A represents an n-valent residue obtained by removing n alcoholic hydroxyl groups from a phosphorus compound having at least n alcoholic hydroxyl groups, where n is an integer of 2 or more.)
And a structural unit (II) represented by
A polyurethaneimide resin characterized by being a phosphorus-containing polycarbonate polyol characterized in that the terminal group is an alcoholic hydroxyl group. The polyurethane-imide resin according to claim 1, wherein the phosphorus-containing polycarbonate polyol includes a structural unit represented by the general formula (1).

(In formula (1), A ¹ represents a divalent residue obtained by removing two alcoholic hydroxyl groups from a phosphorus compound having at least two alcoholic hydroxyl groups.)   2. The polyurethaneimide resin according to claim 1, wherein the phosphorus-containing polycarbonate polyol has a number average molecular weight of 500 to 10,000. The polyurethaneimide resin according to claim 1 or 2, wherein the residue A in the phosphorus-containing polycarbonate polyol is represented by the general formula (2).

(In Formula (2), R ₁ represents a monovalent hydrocarbon group, R ₂ independently represents a divalent hydrocarbon group, and each of the hydrocarbon groups may have a cyclic structure in the structure. And may have heteroatoms.) The polyurethaneimide resin according to any one of claims 1 to 4, wherein the hard segment contains any structural unit selected from the group consisting of structural units represented by formulas (H1) to (H4). .

(In the formula, D represents any of a direct bond, —O—, —CH ₂ —, —CO—, and —SO ₂ —). The resin composition containing the polyurethane imide resin in any one of Claims 1-5.   A cured film obtained by curing the resin composition of claim 6.