TW200940603A - Flame resistant polyurethane imide resin, and resin compositions and hardened films thereof - Google Patents

Abstract

This invention provides polyurethane imide resin with improved flame resistance, and resin compositions and hardened films thereof. The polyurethane imide resin includes a soft segment consisting of polycarbonatepolyol and a hard segment with imide bond, where the polycarbonatepolyol includes a structural unit (I) expressed by a formula: -OCOO- and a structural unit (II) expressed by a residue A (A represents n valent residues obtained by removing n alcoholic hydroxyl groups from phosphorus compounds containing at least n alcoholic hydroxyl groups and n is an integer, n ≥ 2), with an alcoholic hydroxyl group as a terminal group.

Description

200940603 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a polyamine phthalate imide resin having improved flame resistance, comprising: a soft segment composed of a polycarbonate polyol, And a hard segment having a quinone imine bond or a quinone imine bond and a guanamine bond; characterized in that the polycarbonate polyol contains a phosphorus atom in a molecule. Further, the present invention relates to a resin composition containing the above polyamine phthalate imide resin, and a cured film obtained by curing the resin composition. ❹

[Prior Art] [0002] A resin having both softness and heat resistance, comprising a soft segment derived from a polycarbonate polyol, and having a ruthenium bond, or a ruthenium bond and a guanamine Various proposals have been made for the polyurethane quinone imine resin composed of the hard segment of the bond. [0003] Patent Document 2 Patent Document 2 is a towel, which contains a soft bond segment having a carbon bond, and has a hard segment of the amidoxime subfamily and is composed of a polycaptamine imine resin. v [0004] The base of the thief-like singularity of the yelling of the imine violent stimuli = ^ 权 权, secret touch _ (· poly-amine tree [Patent Document 1] 曰本特开平u - 12500 bulletin [Patent Literature [Patent Document 3] JP-A-2002-145981 (Patent Document 4) Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. ), [0005] imine resin, in addition to softness and heat resistance, such polyurethane bismuth, low 3 200940603 -, electric insulation, printing, solder resistance, resistance to veins and mechanical strength, etc. It is suitable for insulation protection of a resin composition such as a flexible substrate. However, these polyamine phthalate imide resins, resin compositions and cured films have room for improvement in flame resistance. 0006] That is, the object of the present invention is to provide a polyurethane bismuth imide resin, a tree I 曰 composition and a cured film, which can provide flexibility in terms of an insulating protective film for a flexible substrate. Heat resistance, low warpage, electrical insulation, printability, solder resistance, Various properties such as resistance to various agents and mechanical strength are not lowered, and flame resistance is improved. (Method for Solving the Problem) 0007 The present invention relates to the following matters: [0008] 1. A polyurethane coating The amine resin comprises: a soft segment composed of a polycarbonate polyol, and a hard bond segment having a thiamine bond; and the polycarbonate polyol comprises: a formula: an OCOO- The structural unit (I) and the residue A (only, A represents an η-valent residue obtained by removing n Q alcoholic hydroxyl groups from a phosphorus compound having at least n alcoholic groups, where η is 2 or more Integer.) The structural unit of (II); 乂. and the terminal group is an alcoholic hydroxyl group. [0009] In other words, the polyamine phthalate imide resin of the present invention comprises: using a polyphosphate containing a molecule in the molecule The soft segment formed by the carbonate polyol and the hard segment having the yttrium II. [0010] 2. The polyurethane amide imide resin according to the above 1, wherein the aforementioned polycarbonate-containing polycarbonate The alcohol contains a structural unit represented by the formula (1). [0011] (1) 200940603 [Chemical]

-0-C-0- ❹ Ο Ο

0 0 _N— Η IN— (In the formula (1), A1 represents a divalent residue after removal from at least 2 ^-based thiol groups.) The alcoholic light-based lining compound will have two alkyd vinegars more than _, Wherein, the phosphorus-containing polycarbon [0012] amount, 45GG to 1〇_. [化] 0 —R2~f—R2— (2)

'Rl' in Ri j(2)! The valence hydrocarbon group, & independently, indicates that the divalent hydrocarbon group can have a cyclic structure or a hetero atom in the structure. The polyurethane amide imide resin according to any one of the above 1 to 4, which comprises any one of the groups consisting of structural units represented by the formulas (H1) to (H4) [0014] [Η] (Η 1) (H2) 200940603

(where 'D denotes a direct bond,—any one). —CH2 — ' —CO— ' —so2 [oot kind resin composition, comprising the above 1 to 5 polyurethane urethane resin. The cured film is obtained by hardening the resin composition of the above 6. Further, in the present invention, "polyurethane phthalimide resin" is a polyamine phthalate tree = and is = more chain domain: a resin having a thiamine bond formed in the formation (denatured polyurethane vinegar tree) The 'aniline bond' is a type of ortho-imine ring. The polyamine phthalate medicinal resin of the present invention can be composed of "an imine bond and a guanamine bond". It is preferred that the ring form an aromatic ugly imine ring together. (Effect of the invention) [0017] The vacancy is obtained, and the polyamine phthalic acid resin is contained in the fluorene The soft key segment and the hard segment having the yttrium imine bond constitute 'improvement of flame resistance. [0018] That is, according to the present invention, the composition of the ten fats and the gifts are given, Af

A polyurethane urethane resin can be obtained, which is required to provide flexibility, electrical insulation, printability, solder resistance, and solvent resistance 200940603 as an insulating protective film for a flexible substrate, and to improve combustion resistance. Various characteristics such as properties and mechanical strength are not lowered. [Embodiment] (Best Mode for Carrying Out the Invention) [0020] In the following description of the alcoholic hydroxyl group, for the sake of simplicity, "at least" The compound is appropriately described as a phosphorus compound Α(ΟΗ)η. [0021] Ester polyol The polyurethane phthalimide resin of the present invention comprises a soft segment composed of polycarbonate and a hard segment having a quinone bond, and is characterized in that: polycarbonate polyol The alcohol comprises: a structural unit (I) represented by the formula: -〇coo-, and a residue Α (only, Α represents a η-valent enthalpy of the η-petal impurity removed from a scaly compound having at least n alcoholic hydroxyl groups, Here, η is a structural unit represented by 2 or more (II); the terminal group is an alcoholic hydroxyl group. [0022] Conventionally, a polyurethane resin is obtained by reacting a polycarbonate polyol constituting a soft segment with a polyvalent isocyanate constituting a hard segment. [0023] The polyurethane amide imide resin of the present invention, the soft segment is formed using a polycarbonate polyol (preferably a polycarbonate diol), but the hard segment is, for example, 1 is used to make the polyisocyanate a method in which a trifunctional or higher polyhical acid or a derivative thereof is reacted to form an oximine bond (or a quinone bond and a guanamine bond) in a hard segment, or (along a polyisocyanate and a quinone bond are included) (or The reaction of the polyol formed by the quinone imine bond and the guanamine bond is formed by turning on the hard 200940603. The method of forming the hard segment is not limited. However, it can be appropriately adopted as #八【0025】 More than 4 hair-imine resin' constitutes a soft segment of the shirt: OCOO — ❹

The structural unit (I) ' and the n-valent residue after the residue A ί n n are represented, where n is an integer of 2 or more. Indicates the structural unit (Π), [002^ end-based scaly nature of phosphorus-containing polycarbonate polyol, can be easily obtained. The charcoal acid has more than 3 soft-bonded segments of the polyamine-based imine resin, which is used in the form of: OCOO- ❹ ( (4) café material level (pre-oxyl group), and with residual [0027] = also =: better than: good. It is 2, 3 and 4. In particular, (1): 3, when there is a residue A of η 2, the scaly polycarbonate polyol contains the general formula (1) 200940603 [0030] [Chemical] / 1 9 + A-0-C- 0- indicates the structural unit. Here, 'A1' denotes a divalent residue obtained by removing two alcoholic groups from at least two alcohol compounds. &基基嶙 [0031] 1 In the case where the polymer chain contains n or more of residue A, the branching occurs in the polymer chain. Force, ❹ ❿ [0032] [Chemical] 2 O-COO - A-O-CO-O-

I o-co-o- base to (four) 3 (four) 嶋 伽 3 3 alcohol [0033] ^ When A is present in the polymer chain, A is bonded to η structural units, and, when present at the end of the polymer And forming at least one hydrazine and at least one constituting a terminal alcoholic thiol group. () [0034] The residue A contained in the phosphorus-containing polycarbonate polyol may be the same or different. When they are different, they may contain residues N which are different from each other, and may contain residues A which are different even if the structure is different from η. 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, the phosphorus compound Α(〇Ή)η is preferably η alcoholic hydroxyl groups. [0036] 9 200940603 The phosphorus-containing polycarbonate carrier used in the present invention may optionally contain residue B derived from sulphate. Residue B, in a general polycarbonate, is bonded to a structural unit of 〇c〇〇, and is a residue contained in the polymer, for example, removed from the polyol used for the purpose of f-blocking acid. The residue after the H group. Usually, it is a divalent residue, a single branch structure, and a residue having a valence of 3 or more. When the residue B is divalent, the structure is [0037] B-0-C-0- ❹ ❹ , which is contained in the polycarbonate polyol containing lin. [0038] If the second method], the east base of the polycarbonate polyol containing the sarcophagus means that the material of the direct bond is secret. Here, the carbon of an aromatic ring member such as an alcoholic benzene ring. ^, 日, that is, not directly bonded to the constituent elements other than the constituents of the carbon atom-bonded H aliphatic group, the aliphatic group or the alicyclic hydrocarbon group, and also the hydroxy group or the alicyclic ring The domain-particular fine oxygen, sulfur n-throwing base ' can also be an aliphatic hydrocarbon group [〇〇4〇] inflammation. The [J?r group] is more preferably a warp group which can be represented by the following chemical formula.

—CX2—OH (X is independently, and is a chlorine atom [0042]. The inverse number 1 to a monovalent hydrocarbon group of hydrazine.) The scaly polycarbonate polyol 卩OH group, or in the case of coexistence, is a bond The residue at the residue A is the 200940603 OH group of the residue B derived from the 7C alcohol component. [0043] Thus, the phosphorus-containing polycarbonate polyol comprises a structural unit (1), a residue A, a structural unit (II), and a residue B as an arbitrary structural unit, preferably substantially only The child is composed. And, the terminal base - A 〇 H (that is, the alcohol group bonded to the residue A), and in the presence of the residue B, has - B 〇 H (that is, the alcohol which is bonded to the residue B) , base)' is preferably essentially only composed of such. Therefore, when both residue A and residue B are both 21, more poly-carbons are extracted, with residue A or residue B and the parent of the early (I) repeating structure 'and the end is an A〇 [ 0044】 Λ 聚 Polycarbonate is intended to be promoted by the residue A. Therefore, it can be 1/〇, that is, there can be no residue. The residue squaring compound A (〇H)n ' is not particularly limited as long as it is a phosphorus atom-containing phosphorus compound. A phosphine compound represented by the formula (3) having two alcoholic alcoholic hydroxyl groups or a phosphorus-based polyol compound represented by the formula (4). The phosphine compound can be obtained from the viewpoints of the ease of use, the operability, and the reactivity of the general formula (5). "Car is better to use the general formula (3) as shown in [0046] [Chemical] 0 ho~r2 - Ρ - r2-oh (3) R1 ~: ^ = = =, preferably carbon number i alkyl), Or an aromatic-containing valence aliphatic hydrocarbon group having a carbon number of ό20 (preferably a hydroxyl group) each independently represents a divalent cigarette, and a "smoke base" 2 is bonded to an alcohol 2 to 25 More preferably, it is 2 to 18, particularly preferably 2 = 6, preferably a carbon number of 1 to 25, more preferably an alkylene group, or a carbon number of 6 to 2f): a divalent aliphatic hydrocarbon group (It is preferably a bivalent hydrocarbon group containing a riding ring, and the former 200940603 can have a ring structure in its structure, and can also have n, s, ◦, etc. [0047] r ίΐίΐ (3) Preferred examples of the compound of the cylind are, for example, n-butyl-bis(3-ΐΪί unicorn, n-propyl-bis(3-propylpropyl)phosphine oxide, ethyl-bis-mt) oxidized lin, phenyl-double (2-hydroxyethyl) phosphine oxide, methyl-bis (Liu ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο Phosphine oxide can be obtained from the Japanese chemical industry limited company, the company's commercial product ΡΟ-4500, so it is suitable [0049] w 〇

/R4-OH (4) ^3-〇-Ρ-〇Η2~Ν; ? 'r4-oh r3 ❹ number m's each of the individual carbons of 1 to 20 carbon atoms (preferably If it contains iL 1 1 to 6 of the 1 valent aliphatic smoky group, or carbon number 6 to 20 contains ί ί ί ϊ 1 ), these may have _ or 赖 in the base, and may also have a carbon number of 1 f ιχϋ A 2-valent hydrocarbon group having a carbon number of 1 to 20 (preferably containing Guan Xingjing, especially Wei 1 to 6 2 彳 职 烃, or a carbon number 6 to 20 containing ίί) 2 2 valent nicotine) 'These may have a _ or vinegar bond in the base, and may also be a specific example of the aminophosphine-polyol represented by [0050] US-==(4), for example: diisopropyl-perylethyl) Silk methyl vinegar, diisobutyl-hydrazine, hydrazine-diaminomethylphosphine, dioctyl·'Ν, Ν-bis(2-cyanoethyl) j, octadecyl- Ν, Ν-bis(2-hydroxyethyl)aminomethyl^^, monoethyl-anthracene, anthracene-bis(2-silylethyl)amine-based mesoic acid vinegar, diethyl 12 .200940603 base-N , N-bis(2-hydroxypropyl)aminodecylphosphonate, and the like. Among them, ADEKA Co., Ltd. is commercially available as "AdekaPolyol FC-450"-ethyl-N,N-bis(2-propylethyl)aminodecylphosphonate. [0051] [Chemical] h〇-r5- -〇-P-〇-Rs- or7 ο -〇-P-〇-R6-J-〇R5-〇h (5) 〇❹ (in (5) Each of Rs and R0 is independently and represents a carbon number of 1 to 2 Å (preferably a carbon number of 1 to 18', especially a carbon number i to 6 of a divalent aliphatic smoky group, = a number of 6 to 20 containing an aromatic ring The divalent hydrocarbon group), each R7 independently represents a carbon number! To 18, especially a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a monovalent hydrocarbon group having 6 to 2 carbon atoms of the aroma ring It may be in its structure and may also have heteroatoms such as N, S, and 。. The structure of m and η ' is at least one of them as a condition to an integer of 1000.) ^ ^ [0052] Preferred examples are, for example, Clariant japan Co., Ltd. under the trade name = EX^^QP55()", which is a water-soluble, cryptic oligo squamous multi-component, such as dimethylmethylphosphonate. , phosphorus pentoxide, epoxy bromide and water are produced in a molar ratio of 2:2:8:1. [0053] _ with 3 or more alcoholic radicals of the phosphorus compound A_n, = ~ (5 = unbonded, agglomerated H of the hydrocarbon group with a hydrazine H group of compounds, or the former ~ (5) medium bond a compound having a hydrazine group having a more OH group, and a compound having a OH group, wherein, for example, a compound of the above formula (3) or a compound having a more fluorenyl group, R1 has 0 而言. ϊ and m such as: 4-silyl butyl-bis(3-silylpropyl) phosphine oxide, ginseng (3 difficult ί 3 3, 2: yl ethyl-bis(3-hydroxypropyl) oxidized lin, hydroxyl f soil surface propyl) phosphine oxide, ginseng (2-hydroxyethyl) phosphine oxide, hydroxymethyl 13.200940603 - bis(2-hydroxyethyl) phosphine oxide, ginseng (hydroxymethyl) phosphine oxide. In the first aspect of the present invention, the phosphorus-containing polycarbonate polyol is used in the following manner, and the following formula (6) is used. The polycarbonate having a phosphorus atom in the molecule has an average molecular weight of about 500 to 10,000. Further, it is preferably ^ ( melon + illusion is 〇〇ι~·, [0056] [化] H〇-(-A-〇-C-〇-j--~|-B-〇-C-〇 J-〇H (6) ❹ (wherein A1 and B have the above meanings, m represents a positive integer, and n represents a zero or a positive integer). In the formula (6), m and n represent the ratio of the repeating units in the intramolecular brackets, and the above-mentioned repeating unit is not limited to be blocked. Further, 1 to 100 and η are 0 to 100. [0057] The following 'description of the preparation of the filled polycarbonate polyol used in the present invention [the first method] to make the polycarbonate polyol, and the phosphorus compound A (〇H) n (especially n == 2 In this method, the same applies to the following description.) The transesterification reaction is carried out. In this reaction, if necessary, H may further add a 2-valent alcohol compound to the reaction. [0058] Polycarbonate polyol, by formula (7) The above-mentioned polymeric acid ester diol is preferred. However, in the formula (7), 'R represents an alkylene group having a carbon number of 2 to 25 (preferably 2 to ls), and k represents an integer of the formula (9). The diol can be produced by any method as long as it is a known method. For example, a divalent alcohol having a carbon number of 4 to 25 (preferably 4 to 15) equivalent to R of the formula (7) can be used. 〇-r-〇h) a transesterification of a carbonate compound with a carbonate compound, a slave number of 2 to 25 (preferably 2 to 15) of a cyclic carbonate having a stretching group: or the aforementioned fat Manufactured by a reaction of a quinone alcohol with a chloroformate or a phosgene, etc., wherein the carbon number of 4 to 25 (preferably 4 to 15) is 2 yuan of the alkyl group of 200940603 The polycarbonate carbonate produced by the exchange reaction of an alcohol with a vinegar compound is preferred. The carbonate compound, for example, a fat such as a dialkyl carbonate, a diaryl carbonate, a carbonated carbonate or a aryl aryl carbonate. a family or aromatic carbonate (carbonic acid specific and § 'for example: dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, diphenyl carbonate, A Base carbonate, ethyl carbonate, propyl carbonate, and the like. It is also possible to use a copolymerized polycarbonate diol obtained by using two or more kinds of 'merols in combination. ~ [0059] [Chemical] HO- R-0-C-0 -R-0H (7) (in the formula (7), k is an integer from 1 to 150;). [0060] The polycarbonate may also be used as a polycarbonate. This is a good example of the polycarbonate. For example, ETERNAC〇LL made by Ube Industries Co., Ltd. (a ku_y polyol series manufactured by registrar Co., Ltd.), daICEL, IT, PLACCEL (registered trademark) series, etc. A plurality of species or a combination of two or more. Further, the number of polyols of the polycarbonates is preferably 以 ϊ ί = preferably the above, _~_ 〇 is better. Polycarbonate has a small average molecular weight, and the phosphorus is produced. Polycarbon_polyol^ In other respects, when the number average molecular weight is large, the viscosity is high, and [0061] [oUf should be a phosphorus compound Α(〇Η)η, for example, the above (3) to (5) are appropriate. ί Ϊ ' For example, the polycarbonate polyol and the phosphorus compound Α (0 Η) η in a predetermined compound iom-like method, or the fusion of the ore of the minerals 1 and the phosphating AS; The method of the reaction, etc., thereby enabling the ratio of the compound Α(ΟΗ)η to the polycarbonate multi-feed ratio with respect to the phosphorus compound A (〇mn丨~============================================== 0.001 to 10 moles, preferably 〇.〇1 to j Moer' ^ mouth polycarbonate fuel polyol carbonate S is more than enough to feed less When the & is (10) ~ G.5 Moer. The molecular weight is reduced, on the other hand, the addition of two; the polyol phosphorus content is reduced., 3-disc polyester polyol [0064] ο reaction temperature It is 50 to 3 〇 (TC, preferably 5 〇 to 2 WC. The anti-ship force is not particularly limited, for example, gc 'more than 100 to, usually nitrogen, argon, helium, light blunt gas ^. The reaction is carried out. Reaction environment, [0065] ^ In the first method, if necessary, the transesterification system is used to make the carbonated acetal compound and the equivalent diol reverse, to the jia ji stone anaerobic vinegar eve scale = 'newly added transesterification catalyst to make the reaction Jia's total amount of feed, "fresh to the amount of the article" relative to [0066] P is preferably 10 to 1000 ppm. S曰 exchange catalyst 'as long as it can catalyze the above = limit. For example, titanium tetrachloride, The tetra-supplement s is not tin, dibutyltin oxide, ginseng (acetoxime), dibutyltin laurate-butyltin oxide, ginseng (ethylhexanoic acid) butyl soil, laurel, ruthenium Oxygen titanium, titanium tetraisopropoxide, etc.) is particularly preferred. It is used as a reaction raw material in the form of tetrasocyanin (four [0067] ▲, according to the first money. Polycarbonate multi-component | by g 2 = B, then the polycarbon of the formula (7) is doubled, including the base, and when the sample is added to the anti-shore, the internal white enters 2 2 f R -. The alcohol compound recognizes that 'the scaly compound is removed. 16.200940603 [Method 2] - The phosphorus compound A(OH)n (preferably n=2') is the same in the following description. 'Reacts with a carbonate compound or phosgene. In this reaction, a 2-valent alcohol compound can be further added to the reaction if necessary. [0069] The feed ratio is preferably a carbonate compound or a phosgene 〇5 to 1 molar relative to the polyol component (the total amount of the squamous compound A (〇H)n and the further added 2-alcohol. [0070] 碳酸 ================================================================================================== Vinegar (carbonate ° specifically, dimethyl carbon_, diethyl carbonate, di-n-butyl carbonate di-n-butyl carbonate, diphenyl carbonate, nonylphenyl carbonate, ethyl carbon酉 酯 ester, propyl carbonate, etc. [0071] = reaction into a brewing exchange 'can be produced according to the well-known method of producing polycarbonate polyol 5 °, that is, as needed (four) exchange catalyst in the presence of In order to properly prepare the phosphorus-containing polycarbon used in the present invention, the aliphatic or aromatic compound of the i-group is continuously extracted from the acid outside the reaction system. It is not limited to the tin compounds such as oxygen, titanium, tetraisopropoxy, etc. Preferably, in the above, tin tetraoxide, R and Jun 'four', propoxy titanate), dibutyl laurate, dibutyl titanate, tetraisopropyl hexyltin is preferred, but The amount of use of the four-sinter-oxygen-titanium (tetra-n-butylene polyol) such that (4) is exchanged with the catalyst is from 1 to 50 ppm, more preferably from 1 to 1 ppm, relative to the internal standard. 200940603 [0073] Before, S is the condition for the exchange reaction, as long as the target can be produced, but in order to make the target produce with good efficiency, it is better to limit the temple to the lower = f 250 c (especially 110 To 240. The reaction is about 〇α to 2〇hour^^0, and the family becomes 2GmmHg or less under the decompression of Na (four) age, listening, argon, etc.) [0074] ❹ , 2 method, adding a 2-valent alcohol compound to At the time of the reaction, the residue after removal of the alcohol compound hydrazine is contained in the form of the obtained polyhydric alcohol containing hydrazine, which is contained in the form of ^. When the divalent alcohol compound is not added to the reaction, the ruthenium-containing poly = 8 曰The reading does not contain the residue B, and contains the carbon-structured structure and the structural unit (11) represented by the residue A. () [0075] The ancient second method has the ability to Residue A indicates the structural unit (11), which has the advantage of being freely controlled from a low ratio to an example, and as a result, it is possible to manufacture a product having a low phosphorus content to a product of Ma. ❹ [0076] As described in the [Method 1] [Second method], in the above reaction, if necessary, by adding a divalent alcohol compound to the reaction, the residue derived from the divalent alcohol compound can be introduced into the phosphorus-containing substance used in the present invention in the form of residue B. Polycarbonate polyol. [0077] Diol compound, for example: 2-methyl~i, 3-propanediol, u-butanediol, 2,4~heptanediol, 2,2-diethyl- 1,3-propanediol, 2-methyl-2-hydroxy--, diol, 2-ethyl-l,3-hexanediol, 2-methyl-2,4-pentanediol, 2, 2,4 I-based-1,3-nonanediol, 2-diyl-2-ethyl-1,3-propanediol and other compounds in which the alkylene is widely dimethylene; 1,4-butanediol The alkyl group is a tetramethylene group, 1,5-pentanediol, 3-mercapto-1,5-pentanediol, 1>5-hexanediol and the like alkyl group 18.200940603 is Wuya 曱Base compound; 1,6-hexanediol, 2-ethylamide~]< _ ί is rf octyl ΐ化r; i7—“Base: sub-substrate, 1,8-octyl- 2: fluorenyl-hydrazine, 8-octanediol is an eight-compound; 1,9-nonanediol, 1, 1〇-nonanediol, ^-undecandiodedodecane diol, 1,2G- 20 propylene glycol and other long-chain stretched 'cyclohexanediol, 1,4-cyclohexanediol, Cyclohexanol-M-diethanol^-diethanol, 2,2-bis(4-cyclohexyl)propane calcination^7,: Ο% and fragrant ring) compounds, diethylene glycol, triethylene glycol , polyethylene glycol, diethylene glycol, polypropylene glycol, polytetramethylene glycol and other internal carbon atoms of the exothermic group:: part of the compound substituted by sulfur, nitrogen atom; 2,5-tetrahydrofuran decyl alcohol, hydrazine a part of the internal carbon atom of a ring-and-burning group, such as a substituent of oxygen, sulfur or nitrogen, or a part of a penetyl group, forming a ring (alicyclic ring and aromatic ring). [0078] The carbonated alcohol has a number average molecular weight of about from about 500 to 5,000 Å and more preferably from about 5 Å to about 3 Å. Therefore, when the anti-banking is 5 valence (when the amount is outside the target range), that is, the molecular weight is small, the diol is further changed by decompression: entering, and the state of - _ is made to react. A well-known method such as a reaction is preferred to carry out molecular weight adjustment. Further, after the molecular weight adjustment, the residual ester-crossing medium is deactivated by water or a scaly compound (4), butyl, butyl acrylate, dibutyl phosphate, etc. good. [0079] Further, regarding this manufacturing method, the inventor of the present invention has proposed the patent medium PCT/JP2008/62m. ❹ wr ming system [0080] According to the foregoing method for preparing a phosphorus-containing polycarbonate carbonate (preferably, a polyglycol diol), the raw material can completely interfere with the acetonitrile exchange of the compound A (〇H) nf. Reaction, , , , \入!! Polycarbonate polyol molecule. Here, "substantially complete" means 9 % by weight, preferably 95% or more, and more preferably 98% or more. At this point, the reaction mixture can be used. 200940603, GPC analysis of the liquid, and the peak of the phosphorus compound A(0H)n disappears substantially and is easily confirmed. [0081] Therefore, in the production method, the raw material phosphorus compound is 0 Η) η Γ is substantially completely "When the transesterification reaction is carried out, the reaction mixture is directly used as a raw material for producing the polyamine oxime oxime imide resin of the present invention. On the other hand, in the polyurethane resin of the present invention, the hard segment preferably has a structural unit represented by the following formula (Η1) to (Η4): .200940603 [0083]

Ο (Η2)

(Η3)

(wherein D represents a direct bond, a Ο-, a _co_, a S02 - any one.) [0084] The structural units are as follows: 'from a polyfunctional carboxylic acid having 3 or more functional groups or Derivatives and introduced into the molecule. The method for synthesizing the polyamine phthalate imide resin of the present invention is not limited, but as described above, it can be easily obtained according to the conventionally known method or the method (ii). [0086] (if side * 'to make at least}) scaly polycarbonate acetate vinegar compound, 3a) 3 functional to take your alcohol 2) 〇 7 〇 isocyanate on the acid or its derivatives in a solvent The system of 21 .200940603 - ΪΞΪ t containing poly-polyol and polyisocyanate vinegar ^ 20~150C, preferably 60~12〇. After 12 hours of reaction, add 3 Luneng can be rebelled, and its derivative is obtained in 8〇~25 (rc, preferably 12〇~相.c H〇75)~% hour reaction. Alternatively, a catalyst such as an acid or a test may be used. The method of (11) is a method for producing a polyol in which at least a polystyrene polyol having a broken polyacetate polyol is present in a solvent. The reaction ' can be formed by argon-bonding a phosphorus-containing polycarbonate polyol to form a multi-component diol component, and the ray is different from the test, preferably 6 〇 to 12 (rc reaction. · Bu 12; 20-20 carbonic acid) Vinegar multi-component _ multi-Wei _ compound, after the synthesis of the prepolymer in 2G~15GH ' 反应 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 包含 包含 包含 包含 包含 包含 包含 包含 包含 于 于 于 于 于 于 于 于 于 于 于 于 于 于12 (rc is carried out by 丨~hour=long reaction. In this reaction, the usual urethane formic acid can be used for the reaction of [0088], and ϊί polyisocyanuric acid can be used as the diisocyanate. The cyanate molecule may have two isocyanate groups. For example, the diisocyanoline of the fat ❹ H is preferably a phthalic acid group, and the number is 2 to 3. Aliphatic, alicyclic Or aromatic diisocyanide _, specifically, a t t four ίιίί, sf, u-pentamethylene diisocyanate, hexamethylene trimethyl hexamethylene diisocyanate, _ 酉曰, 3 - isocyanate methyl - 3,5,5-trimethylcyclohexane A sulphuric acid S 曰 (isophorone diisocyanate), y - double (isocyano Sour vinegar methyl ', bucket, - two Hexyl ketone diisocyanate vinegar, toluene diisoacetone vinegar, 44, —^, methyl isnaphthalene diisocyanate _, toluidine diisocyanate vinegar, ί二τ本一异政@曰专. 'The block diisocyanate of the diisocyanate compound isocyanate group of the present invention is blocked by a block agent. [0089] In the method of (i), a trifunctional or higher acid or a derivative thereof is used. </ br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br> , 2,3,3,,4,-biphenyltetracarboxylic dianhydride, 3,3,,4,4'-biphenyltetracarboxylic-monoanhydride, 2,2',3,3'-biphenyl Carboxylic dianhydride, 3,3,,4,4,-diphenyl ether tetracarboxylate &quot;phthalic anhydride 3,3,4,4 — 2 stupid block 4 tetrahydro acid dianhydride, 3,3,,4 , 4, diphenyl ketone tetraindole, 2,2-bis(3,4-benzenedicarboxylic anhydride) hexafluoropropane, pyromellitic dianhydride, 1,4 ϋ4: benzenedicarboxylic anhydride) benzene, 2 , 2 — bis[4-(3,4-phenoxydicarboxylic anhydride) — ί , , , , 2,3,6,7-naphthalenetetracarboxylic acid di-hepatic, l2,5,6-naphthalenetetracarboxylic acid Needle, 1,2,4,5 〇if acetamidine, M,5,8-naphthalene four ships, two livers, U-double (2,3-two-rebel benzene, money, four-mirror dianhydride, etc. And the ring sister reads the acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 3_mercapto-4-cyclohexene-i Chuan Er Sf and other four cyclophiles, Preferably, the ones, 'the lack of t, 2, 3, 3 - the tetracarboxylic dianhydride, and the trimellitic anhydride, the polyamine obtained [〇〇 = "imine resin for organic The solubility of the solvent is excellent, so it is preferable. As long as the end of the acid is suitable, the following: == base Ϊ 【化】 〇〇(H5) (wherein, X represents the thiol group of the tetracarboxylic acid After the removal of the amine group, Z represents a divalent lipid, and the radical Y represents the repeat number of the imine structure of the diamine, which represents a 〇~2Gm or a group hydrocarbon group, and η represents a polyfluorene 23. 200940603 [0092] In the &lt;polyurethane-based imide resin, the soft segment is derived from a segment formed from a polycarbonate-containing polyol (preferably a polycarbonate diol), and the hard bond segment is derived from a polyvalent isocyanate compound. And a segment formed of a trifunctional or higher polycarboxylic acid or a derivative thereof, Or a segment formed from a polyisocyanate compound and a steroid containing a quinone bond. [0093] One of the polyamine phthalate imide resins produced according to the method of (i) typically has the following structure. , [0094] ❹ [化]

〇 II E-0-C-0

Ο Ο

Here, E represents residue A, residue VIII, residue B, and the like derived from the phosphorus-containing polycarbonate polyol, G represents removal of two hetero-residues from the diisocyanate compound, and X represents a test for continued acid. Remove the residue afterwards. m table == = structure, the number of repetitions. Also, the square brackets [] surrounded by the part, the intention to record the unit. Further, according to the method of (ii), the produced polyamine phthalate imide tree blood has the following structure. [0096]

Here, 'E denotes residue a, A1 'group B, etc. derived from a phosphorus-containing polycarbonate polyol, and G denotes a residue after removing 2 I cyanate J 24 .200940603 from a diisocyanate compound χ He will be the silk of silk after the age of four Wei, γ represents the residue after removal of the amine group, and Ζ represents a divalent lipid or a (tetra) hydrocarbon group. The claws indicate the number of repeats of the polyacetate poly-alcohol structure. n represents an integer of 0 to 20 in the repeating number of the polyimine structure. Moreover, the square bracket [] encloses the part, which means each repeating unit, 2 repeating units, which can be randomly bonded or blocked and bonded. [0097] The two structural formulas shown in '°' are not limited to these, in order to understand the examples of the reactions of 1 and (9). The polyurethane phthalimide resin of the present invention has a total of 1 (8)% by weight, ο chain, 10 to 9 〇% by weight, preferably 2 〇 to 8 〇% by weight, and a hard bond segment of 9 Screaming

Weight, %, preferably 80 to 20 by weight. /〇. This ratio can be easily controlled by the ratio of the raw material components. J [0099] Further, the polyamine bismuth citrate imine of the present invention has a phosphorus content (poly, °·01 ^ , 篁 / 〇 or more, more preferably 1 weight or more 1%) in terms of improving flame resistance. The upper limit of the good rate, which can be seen as the ratio of the hard segment (4), the area of the mosquito, but usually the %

% or less, especially 20% by weight or less. W 〇 [0100] The phosphorus content of the polyamine phthalate imide resin can be easily controlled by using the phosphorus-containing rate as a raw material component. Known scaly poly-carbon polyols' when making poly-carbonic acid-based polyols, the raw material components are preliminarily made into a ratio of phosphorus content, so that these are "reactive and light." The thief is completely confirmed by the GPC measurement of the mixed reaction mixture. ... 匕乂 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 When a resin composition is formed by combining with an epoxy compound or an isocyanide compound 25 200940603, it can be suitably obtained from the above resin composition. Hardened material. [0102] β is introduced into a segment having a reactive group, and is not limited, and for example, a diol compound having a photoreactive group such as a mercapto group or a benzophenanthenyl group or a photoreactive group such as a methacryl group can be used, and the above 1) The compounds of ~3a) or 1) to 3b) can be easily reacted at the same time. ', [0103] The diol compound having a reactive group 'specifically, in the case of a diol compound having a ruthenium, for example, 2,2-bis(hydroxyindenyl)propionic acid, 2,2-di (hydroxymethyl) butyric acid or the like. Further, a diol compound having a phenolic hydroxyl group is exemplified by 2,6-bis-methyl phenol, 2,6-bis(hydroxymethyl)-p-cresol or the like. &quot; [0104] The polyamine phthalate imide resin of the present invention can be used as a filler component such as an epoxy compound or a polyvalent isocyanate compound in an organic solvent, or an inorganic filler, or a hardening catalyst as needed. When combined, a resin composition is appropriately obtained. The resin composition is formed, for example, by printing on the surface of the substrate to form a coating film, and then the coating film is dried and cured by a conventionally known method such as heating or light irradiation, whereby a cured film can be suitably obtained. The cured film is suitably used as an insulating protective film for a flexible substrate, and has various properties such as flexibility, heat resistance, warpage, electrical insulating properties, printability, solder resistance, solvent resistance, and mechanical strength. A hardened film with improved combustion properties. (Embodiment) ❹ [0105] Hereinafter, the present invention will be described in detail by way of examples. Further, the present invention is not limited to the following embodiments. [0106] The measurement and evaluation in the following examples were carried out as follows. [Solid viscosity] The measurement was carried out at a temperature of 25 ° C using a viscometer TV~~20 rotation speed of 10 rpm. [0107] [Initial elastic modulus, elongation, breaking strength] 26 200940603 Minutes ΐ 2 ΐ 离 处理 处理 处理 处理 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 4 u ϋ advance for 60 minutes to heat the treatment to the thickness of the test piece. Use a pull-like sheet sample to cut into a width lcm, a length of 7cm, for the test 2 ^ C ^ ^; T ^ 〇 n UCT-5T), conditions into the test # 十子头速度 5〇mm / min, The distance between the chucks is 5 cm, the initial modulus of elasticity, elongation, and breaking strength. [Volume resistance, surface resistance] ο l〇〇umtK_i ί C The heat treatment was carried out for 60 minutes, and the thickness was measured. °*like. This sheet sample was used as a test piece, and coated on a glass plate having a surface-treated surface in accordance with JIS C2103 [0109] [oxygen index] 八 eight-error solution. . Perform 30 heat treatments, then heat treatment at 12 ° C_60 * clocks to obtain a thickness of about - sheet, pattern. This sheet sample was used as a test piece in accordance with JIS K7201 ra μ*. However, the sheet sample of the present invention was soft and not self-supporting, and the oiol sample was fixed to a metal frame having a width of 38 kW and a height of 120 mm for measurement. [Low warpage] The resin composition of the sample was applied to the surface of the U-ray's (UPILEX35SGA) made by Ube Industries Co., Ltd. to form a coating film, which was heated at 8 °C for 3 minutes, followed by 120 C was heated for 60 minutes to form a thick hardening of ι〇μιη: the laminated body of the obtained polyimide film and the cured film was cut into a positive shape of 5 cm x 5 cm, and used as a test piece, and this was equal to a hardened film on a horizontal surface. The top surface is placed in the shape of the top surface, and the height of the four angular distances of the test piece is measured. The height average 値 of the four angular distances is obtained as an indicator of warpage. [0111] [Bending property] 27 200940603 Amine film in ? 丝 份 份 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚, forming a sub-if film and a hard tilting product, gauss 2emX width 1 cm = rectangle, for K test &gt; |. Let the test (10) length direction of the towel, bend and heavy ^ make the hardened film become inside 'in its bend The department is 5 〇〇g stone to code, and is allowed to stand for i minutes. After == ί, the test piece is folded into a microscope, and no abnormality is recorded as 〇, and when cracks and whitening are observed, it is recorded as X. [0112] [Difficult Flammability (UL94V-0)] 涂布 The resin composition of the sample was applied to the table φ ' of the polyimine film (UPILEX35SGA) made by Ube Industries, Ltd. to form a coating film, which was carried out at 8 ° C for 3 minutes. The addition treatment was followed by heat treatment at 120 ° C for 60 minutes to form a thick layer of 1 μμηι hardened f. The laminate of the obtained polyimide film and the cured film was cut into a length of 5 inches and a width of 0.5 inches. The rectangular shape is used as a test piece. [0113] The evaluation of the upper flame resistance is carried out in accordance with the UL94 specification vertical burning test method. The test piece is fixed in the vertical direction to the pedestal of the clamp, and the upper part is fixed by the clamp so that the lower end thereof becomes 12 inches (304.8 mm). Further, in order to confirm the fire when the Mars falls, the absorbent cotton is placed under the sample. In the center of the lower end of the test piece, the flame is adjusted to a flame of 0/75 inch (19.05 mm). After 1 second (the part below the sample is 1 inch (25.4 mm)), the flame is removed. The burning time of the sample. Immediately after the fire, the flame was contacted for 10 seconds, and the combustion (red heat) time was measured. The measurement was performed with η == 5 as the first group, and two groups of tests were performed (1 point). 'Confirm the following items. All of these items are qualified. Soil (1) After the first contact with the fire, it does not continue to burn for more than ίο seconds (2) 5 points χ 2 times (10 points) after exposure to flame, burning time Within 5 sec (3) Mars dripping, not burning cotton under 12 inches (4) Red hot burning time after the second contact fire is less than 30 seconds (5) Not extended to the clamp Department 28 .200940603 [0114] [solid content concentration] The sample solution weight Wl (g) is placed in an aluminum dish. 15 (TC was dried by heating for 4 hours) 'Measure the dry sample weight W2 (g). The solid content concentration was determined from χ(%) = W1/W2xl00. [0115] [Hydroxyl price] according to JIS-K-1557 [0116] [Reaction rate of phosphorus compound (GPC measurement)] LC LC-10 (GPC column KF - 80Mx2, KF-802) manufactured by Shimadzu Corporation Ltd. 'Measurement with THF as solvent A standard sample of ethylene was used to determine the number average molecular weight. [0117] The compounds used in the following examples are shown below. [Construction compound] HISHICOLIN PO — 4500 (made by Nippon Chemical Industry Co., Ltd., n-butyl-bis(3-hydroxypropyl)phosphine oxide) [polycarbonate diol] ❹ KURARAY polyol C-5090 (KURARAY limited stock) Company, hydroxyl price 22.6mgKOH/g) ETORNACOLL UH-CARB100N (made by Ube Industries, Ltd., hydroxyl price 110mgKOH/g) [Transesterification catalyst] Siyi n-butoxide (made by Wako Pure Chemical Co., Ltd.) [Catalyst deactivating agent] Di-n-butyl phthalate (made by Wako Pure Chemical Co., Ltd.) [Polyciic acid derivative] 29 200940603 [Diamine compound] . Isophorone diamine (Wako Pure Chemical Co., Ltd.) Co., Ltd.) [A monoamine with one alcoholic base] 3 - Aminopropanol (made by Wako Pure Chemical Co., Ltd.) [Chain extender] 2,2 - bis(transmethyl)propionic acid (Guangrong PERSTORP Co., Ltd.) [Multi-component sulphuric acid S-based compound] CORONATE T — 80 (made by Japan POLYURETHANE INDUSTRIAL CO., LTD.) [Organic solvent] γ γ-butyrolactone (made by Wako Pure Chemical Co., Ltd.) Ethanol (made by Wako Pure Chemical Co., Ltd.) [Epoxy compound] EPICOTE 828 EL (made by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 184~194) [Cure catalyst] CUREZOL 2E4MZ (manufactured by Shikoku Chemical Industry Co., Ltd., 2-ethyl-4- 4-mercaptoimidazole) [Filling material] AEROSIL R972 (Specific surface area (BET method) manufactured by AEROSIL Co., Ltd.: 110 m2/g) ® [0118] [Reference Example 1] [Production of phosphorus-containing polycarbonate diol] With a stirrer, a thermometer, and a nitrogen introduction tube 3 〇〇 mL glass reaction vessel, adding C-5090 150.00 g, PO-4500 53.55 g, at 1 Torr. (: stirring for 1 hour to dissolve. After raising the temperature to 16 ° C, add tetra-n-butoxytitanium ruthenium i.g, and mix the reaction for 8 hours. Then, the reaction mixture is cooled to i2 &£ ;c, adding 0.13g of di-n-butyl linal acid ester, stirring for 2 hours to disturb the catalyst to inactivate. [0119] ' By this reaction, the viscosity is 16Pa · s, the hydroxyl value i50mgK〇H / g, The liquid polycarbonate was filled with polycarbonate diol at 20 ° C. It was confirmed by GPC that 98% or more of the original material 4500 was reacted. [_] [Reference Example 2] [Alcoholic hydroxyl group Manufacture of terminal quinone imine polymer solution] 5L glass separable flask with nitrogen inlet tube, DEAN-STARK receiver, cooling tube, and 2,3,3,,4'-diphenyltetracarboxylic acid Anhydride 1471g, ethanol 5〇7g, and γ-butyrolactone 2092g' under a nitrogen atmosphere, 90. (: stirring for 1 hour to stir the reaction. Then, adding 3 -aminopropanol 376g to the reaction mixture, different Buddha _ 426g of diamine, heated at 120 ° C for 2 hours and 180 under nitrogen atmosphere. (: 2 φ hours of heating in this state to make the water produced by the hydrazine imidization reaction Nitrogen gas was flowed through the reaction liquid to remove it. [0121] From the above reaction, an alcoholic trans-terminal quinone imine oligomer solution having a solid concentration of 50% was obtained. [0122] [Example 1] [Polyamine citric acid Preparation of the ester imidate (1) In a 300 mL glass reaction vessel equipped with a mixer, a thermometer, and a nitrogen introduction tube, the phosphorus-containing polycarbonate diol obtained in Reference Example 1 was added to 37.5 〇g, © COR〇NATET. - 80 13.20 g, γ-butyrolactone 50.69 g, and stir-flow at 80 ° C for 2 hours to react. Add 2,3,3,,4, biphenyltetrahydro acid, liver, 7.36 g to the reaction mixture. Y-butyrolactone 7.36 g was heated to 160. After stirring, the reaction was stirred for 4 hours. [0123] After the completion of the reaction, 11.82 g of γ-butyrolactone was added to obtain a solid concentration of 46% by weight and a viscosity of 89 Pa.s + A solution of the amine oxime imine (1) having a phosphorus ratio of 2.35 wt%. [0124] Using a solution of the polyamine phthalate imine (1), a flake sample was prepared, and the polyacetamide H曱 imine was determined. (1) Mechanical properties (initial modulus, elongation, breaking strength), electrical insulation (volume resistance, surface resistance), oxygen index. As shown in Table 1. 31 200940603 [Example 2] [Production of Polyurethane Nitrate (2)] Manufactured with a mixer, a thermometer, and a nitrogen gas introduction tube The reaction vessel was charged with 37.50 g of a polyethylene glycol-containing diol obtained in Reference Example 1, 13.21 g of CORONATET-80, and 69 g of γ-butyrolactone, and the mixture was stirred at 80 ° C for 2 hours to carry out a reaction. To the reaction mixture, 4.80 g of trimellitic acid liver and 4.80 g of γ-butyrolactone were added to the temperature of 160 ° C, and the mixture was stirred for 4 hours to cause a reaction. By this reaction, a solution of a polyamine phthalate imine (2) having a solid concentration of 50% by weight, a viscosity of 28.4 Pa·s, and a bismuth phosphorus ratio of 2.46% by weight was obtained. The results of the mechanical properties, electrical insulating properties, and oxygen index of the polyamine phthalate imine (2) measured in the same manner as in Example 1 are shown in Table 1. [Example 3] [Production of polyamine phthalate imine (3)] In a 300 mL glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, the phosphorus-containing polycarbonate obtained in Reference Example 1 was added. 37.50 g of ester diol, alcoholic hydroxy terminal quinone imine oligomer solution obtained in Reference Example 2 〇.4〇g, 2,2-bis(hydroxyindenyl) ® propionic acid 0.86g, CORONATET-80 10.35g 48.86 g of γ-butyrolactone was stirred at 60 ° C for 2 hours, then heated to 80 ° C, and stirred at a temperature of 80 ° C for 4 hours to cause a reaction. By this reaction, a solution of a polyamine phthalate imine (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. The mechanical properties, electrical insulating properties, and milk index results of the polyurethane imidate (3) measured in the same manner as in Example 1 are shown in Table 1. [0131] 32.200940603 - [Comparative Example 1] [Production of polyamine phthalate bismuth iodide (4) containing no phosphorus atom] A 300 mL glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube. Polycarbonate diol UH-CARB1〇〇N 〇〇g, CORONATET-80 35.22 g, γ-butyrolactone i 29.49 g, containing no scale atoms, was added at 80. (: The reaction was stirred for 2 hours. To the reaction mixture, 29.44 g of 2,3,3,4,_biphenyltetracarboxylic dianhydride and 29.44 g of y-butyrolactone were added, and the temperature was raised to 16 (rc, The reaction was carried out by stirring for 4 hours. [0132] By this reaction, a solution of a polyamine phthalate imine (4) containing no saponin having a solid concentration of 51% by weight and a viscosity of 26 Pa.s was obtained. The mechanical properties, electrical insulating properties, and oxygen index of the polyurethane-free imidazole (4) containing no antimony atom were measured in the same manner as in Example 1. The results are shown in Table 1. [0134] Example 4] [Production of Polyurethane Resin Composition Containing Liner Atom] A solution of the polyamine phthalate imide (1) obtained in Example 1 was compared with polyamine citrate 1 part by weight of quinone imine solid component, 5 parts by weight of epoxy resin 828EL, 0.5 part of curing catalyst 2E4MZ, and uniformly stirred and mixed. Further, 7 parts by weight of AEROSILR972 as a filling material is added and mixed, and then used. The drum was kneaded to obtain a polyamine phthalate ylide resin composition. [0135] The resin composition was measured by a rotational viscometer. Further, regarding the cured film composed of the resin composition, mechanical properties (starting modulus, elongation, breaking strength), warpage, bending, electrical insulation (volume resistance, surface resistance), and flame retardancy The results are as shown in Table 2. [Comparative Example 2] [Production of Polyurethane Resin Composition Without Phosphorus Atom] Comparative Example 1 was used. The polyamine phthalate imine (4) containing no phosphorus atom was subjected to the same procedure as in Example 4 except for the use of a phosphorus atom-containing polyamine phthalate imide resin composition. 0137] This resin composition was evaluated in the same manner as in Example 4. The results are shown in Table 2.

Shown. Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Phosphorus content 10 rpm (wt%) 2.35 2.46 2.48 0 Initial modulus of elasticity (MPa) 812 375 35 238 elongation (%) 332 280 536 334 fracture Strength (MPa) 51 21 7 37 Volume resistance (Ω · cm) &gt;lxl〇16 &gt;1χ1016 &gt;1χ1016 &gt;1χ1016 Surface resistance (Ω) &gt;1χ1016 9xl〇15 &gt;1χ1016 &gt;lxl〇16 Oxygen index 33 35 35 22 [0139] Table 2 Example 4 Comparative Example 2 Solution Viscosity (Pa · s) 97 8 Initial Elasticity (MPa) 670 386 34 • 200940603 1 One 丨 - ι· , Elongation (%) 215 196 Breaking strength (MPa) 38 48 Low lightness (mm) &lt;0.5 &lt;0.5 Bending 〇〇Volume resistance (Ω · cm) &gt;1χ1016 &gt;lxl016 Surface resistance (Ω) 5xl〇15 5xl015 Flame retardancy UL94V-0 Qualified unqualified [0140] From the above examples and comparative examples, the polyamine phthalate quinone imide resin of the present invention and its composition have excellent bendability, low warpage, and electrical insulation ( Volume resistance, surface resistance)' At the same time, it is clear from the measurement results of oxygen index and flame retardancy (UL94V-0) that the flame resistance is changed. . (Industrial Applicability) According to the present invention, it is possible to provide a polyamine phthalate imide resin, a resin composition thereof and a hardened crucible, which can provide flexibility and heat resistance as an insulating protective film for a flexible substrate. Various properties such as properties, low warpage, electrical insulation, printability, solder resistance, solvent resistance, and mechanical strength are not lowered, and flame resistance is improved. As a result, since the flame resistance of the flexible substrate is improved, the safety performance of an electronic device such as a flat panel display, a mobile phone, or a personal computer using the flexible substrate is greatly improved. 35 , 200940603 [Simple description of the diagram] None [Key component symbol description] None

Claims (1)

200940603 VII. Patent application scope: 1. A polyurethane bismuth imide resin, and a yttrium imine bond comprising: a hard segment composed of a polycarbonate polyol; a soft segment composed of drunk , characterized by: Polycarbonate S is a polyol containing a structure represented by the formula: -〇c〇〇 - you smashed, made a unit (11); with a residue A (only, a represents from and to a small alcohol After the removal of the sexual lining, the hybrid of the fused silk is represented by the η —, — — domain in which η is an integer of 2 or more. A polycarbamate phthalimide resin according to the item 1, wherein the structural unit represented by the formula (1) is contained: the terminal group is an alcoholic group. 2. For example, the patented range of phosphorus-containing polycarbonate polyols, [Chemical] 0) 1 9 A-0-C-0· Alcoholic silks _ one of them, 4. If the scope of application for patents! Or a polyaniline quinone imine resin of 2, wherein the residue A of the phosphorus-containing polycarbonate polyol is represented by the formula (2): Ο-R2--P-R2- (2) Ri (In the formula (2), 'R! represents a monovalent hydrocarbon group, and R2 independently represents a divalent hydrocarbon group, and any of the hydrocarbon groups may have a cyclic structure in the structure or may have a hetero atom). The urethane ylide resin of any one of claims 1 to 3 wherein the hard segment is selected from the formulas (H1) to (H4) The structural unit 37 .200940603 constitutes any structural unit in the group: * [化] ❹ (H1) (H 2) (H 3) 0 0 Η Ν—(Η4) Ο (where D is not directly bonded, _Ο_, one CH2—, one CO—, one S〇2 _ ). 6. A resin composition comprising the polyamine phthalate imine resin of claims 1 to 5. 7. A cured film obtained by hardening a resin composition of claim 6 of the patent application. 38 200940603 IV. Designation of representative drawings: (1) The representative representative of the case is: No (2) Simple description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: no