CN118043369A - Thermosetting resin, composition, uncured molded article, partially cured molded article, and method for producing thermosetting resin - Google Patents
Thermosetting resin, composition, uncured molded article, partially cured molded article, and method for producing thermosetting resin Download PDFInfo
- Publication number
- CN118043369A CN118043369A CN202280064680.6A CN202280064680A CN118043369A CN 118043369 A CN118043369 A CN 118043369A CN 202280064680 A CN202280064680 A CN 202280064680A CN 118043369 A CN118043369 A CN 118043369A
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- CN
- China
- Prior art keywords
- thermosetting resin
- compound
- bis
- molded article
- hydroxyphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 title claims abstract description 205
- 239000011347 resin Substances 0.000 title claims abstract description 205
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 136
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims description 27
- -1 phenol compound Chemical class 0.000 claims abstract description 282
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 63
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 26
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 238000000465 moulding Methods 0.000 claims description 34
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 33
- 238000012360 testing method Methods 0.000 claims description 30
- 229920001169 thermoplastic Polymers 0.000 claims description 29
- 239000004416 thermosoftening plastic Substances 0.000 claims description 29
- 238000005452 bending Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 14
- 125000006353 oxyethylene group Chemical group 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000962 organic group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 claims description 5
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 claims description 5
- 125000004806 1-methylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- LDQYTDPXIMNESL-UHFFFAOYSA-N 2-methyl-4-propylphenol Chemical compound CCCC1=CC=C(O)C(C)=C1 LDQYTDPXIMNESL-UHFFFAOYSA-N 0.000 claims description 4
- LKJWDWUXGCKFPN-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound OC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 LKJWDWUXGCKFPN-UHFFFAOYSA-N 0.000 claims description 4
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 claims description 4
- OAHMVZYHIJQTQC-UHFFFAOYSA-N 4-cyclohexylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCC1 OAHMVZYHIJQTQC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical group C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- XHASMJXNUHCHBL-UHFFFAOYSA-N 4-(1-phenylethyl)phenol Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=CC=C1 XHASMJXNUHCHBL-UHFFFAOYSA-N 0.000 claims description 3
- IJWIRZQYWANBMP-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-propan-2-ylphenyl)propan-2-yl]-2-propan-2-ylphenol Chemical compound C1=C(O)C(C(C)C)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)C)=C1 IJWIRZQYWANBMP-UHFFFAOYSA-N 0.000 claims description 3
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims description 3
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 claims description 3
- 229920005992 thermoplastic resin Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 description 39
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 32
- 229920000049 Carbon (fiber) Polymers 0.000 description 30
- 239000004917 carbon fiber Substances 0.000 description 30
- 239000002904 solvent Substances 0.000 description 30
- 239000000835 fiber Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 20
- 239000010935 stainless steel Substances 0.000 description 17
- 229910001220 stainless steel Inorganic materials 0.000 description 17
- 239000000843 powder Substances 0.000 description 16
- 238000003825 pressing Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- 230000009477 glass transition Effects 0.000 description 14
- 239000012783 reinforcing fiber Substances 0.000 description 14
- 239000013585 weight reducing agent Substances 0.000 description 14
- 239000002131 composite material Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229920001721 polyimide Polymers 0.000 description 11
- 238000002407 reforming Methods 0.000 description 11
- 229930040373 Paraformaldehyde Natural products 0.000 description 10
- 239000004642 Polyimide Substances 0.000 description 10
- 238000005336 cracking Methods 0.000 description 10
- 229920002866 paraformaldehyde Polymers 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 238000004513 sizing Methods 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 238000002411 thermogravimetry Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 5
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
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- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 2
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- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Provided are a benzoxazine-based resin which is excellent in flexibility before curing and/or in decomposition temperature and toughness before and after curing, and a method for producing the same. The thermosetting resin according to one aspect of the present invention is a thermosetting resin having a benzoxazine ring structure in the main chain, which has an aromatic group derived from a difunctional phenol compound (a), a linear alkylene group derived from an aliphatic diamine compound (B), and optionally a (poly) oxyalkylene group derived from a (poly) oxyalkylene diamine compound (C).
Description
Technical Field
The present invention relates to a thermosetting resin having a benzoxazine ring structure in a main chain and a method for producing the same.
Background
It is known that a benzoxazine compound undergoes a reaction such as ring-opening polymerization of a benzoxazine ring by heat or the like, and cures without generating volatile components. Therefore, thermosetting resins containing a low-molecular compound or a polymer having a benzoxazine structure as a main component have been attracting attention, in addition to basic characteristics of thermosetting resins such as heat resistance, water resistance, chemical resistance, mechanical strength and long-term reliability, and various advantages such as low dielectric constant and low cure shrinkage. Among them, low molecular weight compounds having a benzoxazine structure are easy to produce, but have characteristics such as being brittle in an uncured solid state and poor in operability. In addition, although the polymer having a benzoxazine structure is excellent in handleability in an uncured solid state, it has characteristics such as difficulty in production, and therefore, it is flexible to adopt a corresponding form according to desired characteristics.
Patent document 1 discloses a method for producing a thermosetting resin having a dihydrobenzoxazine ring structure in its main chain by reacting a difunctional phenol compound, an aliphatic diamine or an aromatic diamine, and an aldehyde compound.
(Prior art literature)
Patent document 1: japanese patent laid-open No. 2008-29070
Disclosure of Invention
(Problem to be solved by the invention)
However, from the viewpoint of realizing a benzoxazine-based thermosetting resin excellent in flexibility before curing, there is still room for further improvement in the above-mentioned conventional benzoxazine-based resins. In addition, there is room for improvement in terms of decomposition temperature and toughness before and after curing.
An object of one aspect of the present invention is to realize a benzoxazine-based thermosetting resin excellent in flexibility before curing and a method for producing the same. Another object of the present invention is to provide a benzoxazine-based resin excellent in decomposition temperature and toughness before and after curing, and a method for producing the same.
In order to solve the above problems, the main chain of the thermosetting resin according to one aspect of the present invention has a benzoxazine ring structure represented by the general formula (I).
[ In the general formula (I),
Ar 1 and Ar 2 each represent a 4-valent aromatic group derived from the difunctional phenol compound (A), ar 1 and Ar 2 may be the same or different groups from each other,
N represents an integer of 0 or more,
When n=0, R 1 represents a linear alkylene group having 8 to 12 carbon atoms derived from the aliphatic diamine compound (B), and when n=1 or more, R 1 represents a linear alkylene group having 6 to 12 carbon atoms derived from the aliphatic diamine compound (B),
R 2 represents a (poly) oxyalkylene group derived from a (poly) oxyalkylene diamine compound (C),
In the case where n=0, at least one of the 2 terminals of the main chain is a group represented by the following general formula (II) derived from the monofunctional phenol compound (E), the 2 terminals may be the same or different groups from each other,
N=0, m represents an integer of 2 or more, n=1 or more, m represents an integer of 1 or more,
The repeating units represented by m and the repeating units represented by n are repeated in a random manner, or in a block manner, or are alternately copolymerized. A kind of electronic device
[ In the general formula (II),
X represents a hydrogen atom or an organic group having 1 to 20 carbon atoms,
L represents an integer of 0 to 3. A kind of electronic device
In order to solve the above problems, a thermosetting resin according to one aspect of the present invention is a thermosetting resin having a benzoxazine ring structure in the main chain,
An uncured molded article obtained by molding the thermosetting resin and having a degree of cure of less than 1%, or a partially cured molded article obtained by curing the thermosetting resin and having a degree of cure of 1 to 99%, has thermoplastic reshaping properties and toughness,
The thermoplastic reshaping properties refer to the following properties: the uncured molded body or the partially cured molded body is deformed into an arbitrary shape and then returns to a shape before deformation when heated at 200 ℃ or less,
The toughness refers to the following properties: the uncured shaped body or the partially cured shaped body does not generate a crack or a crack as compared with the heating before and after,
The thermosetting resin has a repeating thermoplastic, which means: the reshaping property and the toughness can be maintained even if subjected to the deformation and the heating more than 1 time.
In order to solve the above problems, a method for producing a thermosetting resin according to an aspect of the present invention is a method for producing a thermosetting resin having a benzoxazine ring structure in a main chain, the method comprising:
Step (s 1) of reacting a difunctional phenol compound (a), an aliphatic diamine compound (B) and an aldehyde compound (D);
an optional step (s 2) of reacting the difunctional phenol compound (A), (poly) oxyalkylene diamine compound (C) and aldehyde compound (D); and
An optional step (s 3) of reacting the monofunctional phenol compound (E),
In the case where step (s 2) is not included, the manufacturing method includes step (s 3),
In the case where step (s 2) is included, the aliphatic diamine compound (B) is an aliphatic diamine having a linear alkylene group having 6 to 12 carbon atoms, in the case where step (s 2) is not included, the aliphatic diamine compound (B) is an aliphatic diamine having a linear alkylene group having 8 to 12 carbon atoms,
The (poly) oxyalkylene diamine compound (C) has a (poly) oxyethylene group and/or a (poly) oxypropylene group.
(Effects of the invention)
According to one aspect of the present invention, a benzoxazine-based thermosetting resin excellent in flexibility before curing can be realized. In addition, according to one aspect of the present invention, a benzoxazine-based resin excellent in decomposition temperature and toughness before and after curing and a method for producing the same can be provided.
Drawings
Fig. 1 is a DMA graph of various films.
Detailed Description
[ 1. Heat-curable resin ]
An example of the embodiment of the present invention will be described in detail below, but the present invention is not limited thereto. Unless otherwise specified in the present specification, "a to B" representing a numerical range means "a or more and B or less". In the present invention, a thermosetting resin that is not heated at all is sometimes referred to as an "uncured resin".
In the example of patent document 1, a phenol-terminated Bz (hereinafter referred to as C6 Bz) having a structural unit derived from an aliphatic diamine (hexamethylenediamine) having 6 carbon atoms is carried. However, the present inventors have found that C6Bz has room for further improvement from the viewpoint of flexibility before curing.
According to one embodiment of the present invention, the present inventors have found that a benzoxazine-based thermosetting resin excellent in flexibility before curing can be obtained by introducing a structural unit derived from an aliphatic diamine having 8 to 12 carbon atoms into a benzoxazine structure. In addition, according to one aspect of the present invention, the present inventors have found that a benzoxazine-based thermosetting resin excellent in decomposition temperature and toughness before and after curing can be obtained by introducing a structural unit derived from an aliphatic diamine having 6 to 12 carbon atoms and a structural unit derived from a (poly) oxyalkylene diamine compound into a benzoxazine structure. Further, by using the thermosetting resin, an uncured molded article having thermoplastic properties even before curing can be obtained. That is, the thermosetting resin may be a thermosetting thermoplastic benzoxazine.
The main chain of the thermosetting resin of the present invention has a benzoxazine ring structure represented by the following general formula (I). In this specification, a thermosetting resin having a benzoxazine ring structure is also referred to as a benzoxazine resin.
[ In the general formula (I),
Ar 1 and Ar 2 each represent a 4-valent aromatic group derived from the difunctional phenol compound (A), ar 1 and Ar 2 may be the same or different groups from each other,
N represents an integer of 0 or more,
When n=0, R 1 represents a linear alkylene group having 8 to 12 carbon atoms derived from the aliphatic diamine compound (B), and when n=1 or more, R 1 represents a linear alkylene group having 6 to 12 carbon atoms derived from the aliphatic diamine compound (B),
R 2 represents a (poly) oxyalkylene group derived from a (poly) oxyalkylene diamine compound (C),
In the case where n=0, at least one of the 2 terminals of the main chain is a group represented by the following general formula (II) derived from the monofunctional phenol compound (E), and the 2 terminals may be the same or different groups from each other,
N=0, m represents an integer of 2 or more, n=1 or more, m represents an integer of 1 or more,
The repeating units represented by m and the repeating units represented by n are repeated in a random manner, or in a block manner, or are alternately copolymerized. A kind of electronic device
[ In the general formula (II),
X represents a hydrogen atom or an organic group having 1 to 20 carbon atoms,
L represents an integer of 0 to 3. A kind of electronic device
In the general formula (I), ar 1 and Ar 2 represent a 4-valent aromatic group derived from a difunctional phenol compound (a). As the difunctional phenol compound (A), it preferably has a structure such that its OH group and the group ortho to the OH group are bonded to the benzoxazine ring.
Examples of the difunctional phenol compound (A) include a diphenol compound, a dihydroxydiphenyl ether, a dihydroxydiphenyl methane compound (including derivatives, the same applies hereinafter), a dihydroxydiphenyl ethane compound, a dihydroxydiphenyl propane compound, a dihydroxydiphenyl butane compound, a dihydroxydiphenyl cycloalkane compound (for example, a dihydroxydiphenyl cyclohexane compound), a dihydroxydiphenyl ketone compound, a dihydroxydiphenyl fluorene compound, a dihydroxydiphenyl benzene compound, and other dihydroxydiphenyl compounds (referred to as bisphenol compounds).
In general formula (I), when n=0, examples of the difunctional phenol compound (a) include a diphenol compound, a dihydroxydiphenyl ether, a dihydroxydiphenyl methane compound (including derivatives, the same applies hereinafter), a dihydroxydiphenyl ethane compound, a dihydroxydiphenyl propane compound, a dihydroxydiphenyl butane compound, a dihydroxydiphenyl cycloalkane compound, a dihydroxydiphenyl ketone compound, a dihydroxydiphenyl fluorene compound, a dihydroxydiphenyl benzene compound, and other dihydroxydiphenyl compounds.
In the general formula (I), when n=1 or more, examples of the difunctional phenol compound (a) include a diphenol compound, a dihydroxydiphenyl ether, a dihydroxydiphenyl methane compound, a dihydroxydiphenyl ethane compound, a dihydroxydiphenyl propane compound, a dihydroxydiphenyl butane compound, a dihydroxydiphenyl cycloalkane compound, a dihydroxydiphenyl ketone compound, a dihydroxydiphenyl fluorene compound, a dihydroxydiphenyl benzene compound, and other dihydroxydiphenyl compounds.
Examples of the diphenol compound include 4,4 '-biphenol and 2,2' -biphenol.
Examples of the dihydroxydiphenyl ether include 4,4 '-dihydroxydiphenyl ether and 2,2' -dihydroxydiphenyl ether.
Examples of the dihydroxydiphenyl methane compound include bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) methane (also called 4,4 '-dihydroxydiphenyl methane, bisphenol F), and 2,2' -dihydroxydiphenyl methane.
Examples of the dihydroxydiphenylethane compound include 1, 1-bis (4-hydroxyphenyl) -1-phenylethane and 1, 1-bis (4-hydroxyphenyl) ethane (generally referred to as bisphenol E).
Examples of the dihydroxydiphenylpropane compound include 2, 2-bis (4-hydroxyphenyl) propane (generally referred to as bisphenol A or BPA), 2-bis (4-hydroxyphenyl) hexafluoropropane, 2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-isopropylphenyl) propane, 5'- (1-methylethylene) -bis [1,1' - (bisphenyl) -2-ol ] propane, 1-bis (4-hydroxyphenyl) propane, and 1, 1-bis (4-hydroxyphenyl) -2-methylpropane.
Examples of the dihydroxydiphenyl butane compound include 1, 1-bis (4-hydroxyphenyl) butane and 2, 2-bis (4-hydroxyphenyl) butane (generally referred to as bisphenol B).
Examples of the dihydroxydiphenyl cycloalkane compound include 1, 1-bis (4-hydroxyphenyl) -3, 5-trimethylcyclohexane, 1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), and 1, 1-bis (4-hydroxyphenyl) cyclopentane.
Examples of the dihydroxydiphenyl ketone compound include 4,4' -dihydroxybenzophenone.
Examples of the dihydroxydiphenyl fluorene compound include 9, 9-bis (4-hydroxyphenyl) fluorene and the like.
Examples of the dihydroxydiphenyl benzene compound include 1, 3-bis (4-hydroxyphenoxy) benzene and 1, 4-bis (3-hydroxyphenoxy) benzene.
Examples of the other dihydroxydiphenyl compound include bis (4-hydroxyphenyl) -2, 2-dichloroethylene, bis (4-hydroxyphenyl) sulfone, 1, 3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 1, 4-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 4'- [1, 3-phenylenebis (1-methyl-ethylene) ] bisphenol (three-well chemical "bisphenol M"), 4' - [1, 4-phenylenebis (1-methyl-ethylene) ] bisphenol (three-well chemical "bisphenol P"), and the like.
Among them, 4' -dihydroxydiphenyl ether, bis (4-hydroxyphenyl) methane, 2-bis (4-hydroxyphenyl) propane and the like are preferable, and 2, 2-bis (4-hydroxyphenyl) propane is more preferable.
In the general formula (I), R 1 represents a 2-valent linear alkylene group having 8 to 12 carbon atoms (in the case of n=0) or 6 to 12 carbon atoms (in the case of n=1 or more) derived from the aliphatic diamine compound (B). Specifically, the aliphatic diamine compound (B) includes a diamine compound having a linear alkylene group having 8 to 12 carbon atoms (in the case of n=0) or 6 to 12 carbon atoms (in the case of n=1 or more). In the former case, a diamine compound having a main chain skeleton of 8 to 12 carbon atoms and having a saturated hydrocarbon group is preferable, and for example, 1, 8-octanediamine (i.e., octamethylenediamine), 1, 9-nonanediamine (i.e., nonamethylenediamine), 1, 10-decanediamine (i.e., decamethylenediamine), 1, 11-undecanediamine (i.e., undecanemethylenediamine), 1, 12-dodecanediamine (i.e., dodecamethylenediamine) is preferable. In the latter case (n=1 or more), a diamine compound having a linear alkylene group having 6 carbon atoms is preferable, and for example, 1, 6-hexamethylenediamine (i.e., hexamethylenediamine) is preferable.
In the general formula (I), R 2 represents a 2-valent (poly) oxyalkylene group derived from a (poly) oxyalkylene diamine compound (C) having a (poly) oxyalkylene skeleton and 2 amino terminals. In the present specification, (poly) oxyalkylene includes monooxyalkylene (composed of 1 oxyalkylene) and polyoxyalkylene (containing a plurality of oxyalkylene groups). The (poly) oxyalkylene diamine compound (C) preferably has (poly) oxyethylene and/or (poly) oxypropylene as (poly) oxyalkylene groups. As the (poly) oxyalkylene diamine compound (C), jeffamine D-230, jeffamine D-400, jeffamine D-2000, jeffamine D-4000 of Jeffamine (registered trademark) D-series can be mentioned. Jeffamine D-2000 is particularly preferred. The thermosetting resin of the present invention contains a 2-valent (poly) oxyalkylene group derived from a (poly) oxyalkylene diamine compound, and can improve the toughness of the thermosetting resin before and after curing.
The aldehyde compound (D) may be used in the synthesis of the thermosetting resin of the present invention. The aldehyde compound (D) is not particularly limited, but formaldehyde is preferable, and the formaldehyde may be used in the form of a polymer thereof, i.e., paraformaldehyde, or an aqueous solution thereof, i.e., formalin, or the like.
The monofunctional phenol compound (E) is not particularly limited, and examples thereof include phenol, o-cresol, m-cresol, p-tert-butylphenol, p-octylphenol, p-cumylphenol, dodecylphenol, o-phenylphenol, p-phenylphenol, 1-naphthol, 2-naphthol, m-methoxyphenol, p-methoxyphenol, m-ethoxyphenol, p-ethoxyphenol, 3, 4-dimethylphenol, 3, 5-dimethylphenol and the like. Among them, phenol is preferable.
In the general formula (I), m represents an integer of 1 or more, and is preferably 2 or more, more preferably 3 or more, and even more preferably 5 or more, from the viewpoint of improving the mechanical properties before and after curing. From the viewpoint of maintaining fluidity during molding, m is preferably 500 or less, more preferably 300 or less, further preferably 200 or less, and particularly preferably 100 or less.
In the general formula (I), n represents an integer of 0 or more in terms of polymerization degree, but from the viewpoint of improving flexibility before curing, n is preferably 0. From the viewpoint of improving the mechanical properties before and after curing, n is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and particularly preferably 5 or more. From the viewpoint of maintaining fluidity during molding, n is preferably 500 or less, more preferably 300 or less, further preferably 200 or less, and particularly preferably 100 or less.
When n=1 or more, the ratio of m to n is preferably: n/m=1/0.1 to 1/100. When the ratio of m to n is in the above range, a thermosetting resin excellent in the decomposition temperature and toughness before and after curing can be obtained.
The thermosetting resin of the present invention may contain a structure other than the benzoxazine ring structure represented by the general formula (I). For example, a structure derived from a monocyclic phenol compound in which the terminal of the structure represented by the general formula (I) is blocked may be used. The thermosetting resin of the present invention may contain a structure derived from an aliphatic monoamine or a (poly) oxyalkylene monoamine compound.
Examples of the "organic group having 1 to 20 carbon atoms" represented by X in the general formula (II) include methyl, ethyl, t-butyl, octyl, dodecyl, phenyl, cumyl, methoxy, ethoxy and the like.
In the thermosetting resin of the present invention in the case where n=0, the weight average molecular weight (Mw) measured by GPC is preferably 1000 or more, more preferably 1500 or more, still more preferably 2000 or more, particularly preferably 2500 or more, and particularly preferably 3000 or more, from the viewpoint of improving the mechanical properties before and after curing. In the case where n=0, mw may be 4000 or 5000 or more. When n=1 or more, mw is preferably 10000 or more, and from the viewpoint of improving mechanical properties before and after curing, mw is more preferably 15000 or more. In the case where n=0, mw is preferably less than 10000, more preferably 8000 or less, still more preferably 7000 or less, still more preferably 6000 or less, and particularly preferably 5000 or less, from the viewpoints of availability and workability. When n=1 or more, the weight average molecular weight (Mw) is preferably 100000 or less.
[ 2 ] Process for producing thermosetting resin ]
The method for producing a thermosetting resin according to the present invention is a method for producing a thermosetting resin having a benzoxazine ring structure in its main chain, characterized in that,
Comprising the following steps:
step (s 1) of reacting a difunctional phenol compound (a), an aliphatic diamine compound (B) and an aldehyde compound (D);
an optional step (s 2) of reacting the difunctional phenol compound (A), (poly) oxyalkylene diamine compound (C) and aldehyde compound (D); and
An optional step (s 3) of reacting the monofunctional phenol compound (E),
Wherein, in the case of not including the step (s 2), the manufacturing method includes a step (s 3),
In the case where step (s 2) is included, the aliphatic diamine compound (B) is an aliphatic diamine having a linear alkylene group having 6 to 12 carbon atoms, in the case where step (s 2) is not included, the aliphatic diamine compound (B) is an aliphatic diamine having a linear alkylene group having 8 to 12 carbon atoms,
The (poly) oxyalkylene diamine compound (C) has a (poly) oxyethylene group and/or a (poly) oxypropylene group.
By such a method for producing a thermosetting resin, a thermosetting resin excellent in flexibility before curing and/or excellent in decomposition temperature and toughness before and after curing can be obtained. In addition, the step (s 3) can prevent gelation by blocking the reactive terminal by reacting the monofunctional phenol compound (E). The items described in the section [ 1 ] thermosetting resin are not repeated.
Step (s 1) is a step of reacting the difunctional phenol compound (a), the aliphatic diamine compound (B) and the aldehyde compound (D). By the step (s 1), a unit corresponding to the polymerization degree m shown in the general formula (I) can be produced.
Step (s 2) is a step of reacting the difunctional phenol compound (A), (poly) oxyalkylene diamine compound (C) and aldehyde compound (D). By the step (s 2), a unit corresponding to the polymerization degree n shown in the general formula (I) can be produced.
The step (s 1) and the step (s 2) may be performed simultaneously, the step (s 1) may be performed first, the step (s 2) may be performed further, or the step (s 2) may be performed first, and the step (s 1) may be performed further. That is, the step (s 2) may be performed by adding the material of the step (s 2) to the reaction system after the reaction of the step (s 1), or vice versa. In addition, the step (s 1) and the step (s 2) may be performed in different reaction systems, and then the reaction may be performed by using the same reaction system for the products obtained separately. In other words, the production method of the present invention may include a step of reacting the difunctional phenol compound (a), the aliphatic diamine compound (B), the (poly) oxyalkylene diamine compound (C), and the aldehyde compound (D). In the production method of the present invention, the aliphatic diamine compound (B) and the (poly) oxyalkylene diamine compound (C) may be added simultaneously or sequentially. From the viewpoint of ease of operation, it is preferable that step (s 1) and step (s 2) are performed simultaneously. In the case where step (s 2) is included in the above-described production method, step (s 3) may be included or step (s 3) may not be included.
In the above production method, the step (s 1) of reacting the difunctional phenol compound (a), the aliphatic diamine compound (B) and the aldehyde compound (D) and the step (s 3) of reacting the monofunctional phenol compound (E) may be performed simultaneously, or the step (s 1) may be performed first, and then the step (s 3) may be performed. That is, the step (s 3) may be performed by adding the material of the step (s 3) to the reaction system after the reaction of the step (s 1). From the viewpoint of ease of operation, it is preferable that step (s 1) and step (s 3) are performed simultaneously. The production method according to one embodiment of the present invention may further include a step of reacting the difunctional phenol compound (a), the aliphatic diamine compound (B), the aldehyde compound (D), and the monofunctional phenol compound (E).
In the case where the above-described production method includes steps (s 1), (s 2) and (s 3), steps (s 1), (s 2) and (s 3) may be performed simultaneously, steps (s 1) and (s 2) may be performed simultaneously, steps (s 3) may be performed sequentially, steps (s 1) and (s 3) may be performed simultaneously, steps (s 2) and (s 3) may be performed sequentially, steps (s 1) may be performed sequentially, steps (s 2) may be performed sequentially, steps (s 3) may be performed sequentially, and steps (s 2) may be performed sequentially, steps (s 1) may be performed sequentially, and steps (s 3) may be performed sequentially. In other words, the production method of the present invention may include a step of reacting the difunctional phenol compound (a), the aliphatic diamine compound (B), the (poly) oxyalkylene diamine compound (C), the aldehyde compound (D), and the monofunctional phenol compound (E). In the production method of the present invention, the aliphatic diamine compound (B), the (poly) oxyalkylene diamine compound (C) and the monofunctional phenol compound (E) may be added simultaneously or may be added sequentially. From the viewpoint of ease of operation, it is preferable that step (s 1), step (s 2) and step (s 3) are performed simultaneously.
It is also known that the benzoxazine polymer is poor in stability (storage stability) when dissolved in a solvent, and is easily gelled. The present inventors have found that, in the method described in patent document 1, a monofunctional phenol compound is added to block the reactive end and prevent gelation, but the polymerization reaction to grow the molecular weight is hindered, and thus it is difficult to obtain a benzoxazine having a high molecular weight.
In the production method of the present invention, the ratio of the molar number of the difunctional phenol (a) to the total of the aliphatic diamine compound (B) and the (poly) oxyalkylene diamine compound (C) is preferably: difunctional phenol (a)/(aliphatic diamine compound (B) + (poly) oxyalkylene diamine compound (C))=10/1 to 1/10, more preferably 2/1 to 1/2. If the ratio of the difunctional phenol (A) to the total molar number of the aliphatic diamine compound (B) and the (poly) oxyalkylene diamine compound (C) is in the above range, gelation is less likely to occur at the time of production, and a thermosetting resin having a high molecular weight can be obtained.
In the above production method, when n=0, the molar ratio of the difunctional phenol compound (a) to the aliphatic diamine compound (B) is preferably 1.0/1.0 to 1.0/2.0, more preferably 5.0/10.0 to 7.5/10.0. If the amount is within this range, gelation is less likely to occur during production, and a high molecular weight product is likely to be obtained.
In the production method of the present invention, the molar ratio of the (poly) oxyalkylene diamine compound (C) to the aliphatic diamine compound (B) is preferably: (poly) oxyalkylene diamine compound (C)/aliphatic diamine compound (B) =1/0.1 to 1/100, more preferably 1/1 to 1/9. If the molar ratio of the (poly) oxyalkylene diamine compound (C) to the aliphatic diamine compound (B) is in the above range, a thermosetting resin excellent in the decomposition temperature and toughness before and after curing can be obtained.
In the production method of the present invention, the molar ratio of the difunctional phenol compound (A) to the aldehyde compound (D) is preferably 1/1 to 1/20, more preferably 1/2 to 1/6. If the molar ratio of the difunctional phenol compound (a) to the aldehyde compound (D) is in the above range, a benzoxazine ring can be appropriately formed.
In the above production method, the molar ratio of the aliphatic diamine compound (B) to the monofunctional phenol compound (E) is preferably 10.0/1.0 to 10.0/5.0, and/or preferably 10.0/5.0 to 10.0/7.5. If the amount is within this range, gelation is less likely to occur during production, and a high molecular weight product is likely to be obtained.
In the production method of the present invention, the solvent is not particularly limited as long as it can dissolve the raw material, and examples thereof include: a halogen-based single solvent such as chloroform; a non-halogen hydrocarbon solvent such as toluene; examples of the mixed solvent of the non-halogen hydrocarbon solvent and the aliphatic alcohol solvent include a mixed solvent of toluene and methanol, a mixed solvent of toluene and ethanol, and a mixed solvent of toluene and isobutanol; ether-based single solvents such as Tetrahydrofuran (THF), and the like.
The non-halogen hydrocarbon solvent in the mixed solvent is a hydrocarbon solvent containing no halogen atom and no hetero atom such as oxygen atom, nitrogen atom and sulfur atom, and may be aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon or the like. Among them, toluene and/or xylene are preferable, and toluene is more preferable. The aliphatic alcohol solvent is a compound in which 1 or more hydroxyl groups are bonded to an aliphatic hydrocarbon. Among them, at least 1 (including isomers) selected from methanol, ethanol, propanol, and butanol is preferable, and at least 1 selected from methanol, ethanol, and propanol is more preferable.
The volume ratio of the non-halogen hydrocarbon solvent to the aliphatic alcohol solvent is preferably: (non-halogen hydrocarbon solvent)/(aliphatic alcohol solvent) =50/50 to 80/20.
In the case where n=0, the reaction temperature and the reaction time are not particularly limited, and the reaction may be carried out at a temperature of about room temperature to 120 ℃ or about room temperature to 150 ℃ for several tens of minutes to several hours. In one embodiment of the present invention, particularly, if the reaction is carried out at a temperature of about 30 to 110℃or 30 to 150℃for 20 minutes to 5 hours or 20 minutes to 9 hours, the reaction proceeds smoothly to obtain a polymer capable of exhibiting the function of the thermosetting resin according to one embodiment of the present invention, which is preferable.
When n=1 or more, the reaction temperature in step (s 1), step (s 2) and/or step (s 3) is preferably 25 to 150 ℃, more preferably 40 to 120 ℃. When n=1 or more, the reaction time of step (s 1), step (s 2) and/or step (s 3) is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.
In addition, the water produced during the reaction is also an effective method for promoting the progress of the reaction by discharging the water out of the system. The target polymer can be obtained by adding a large amount of a poor solvent such as methanol to the solution after the reaction to precipitate the polymer, separating the polymer, and drying the separated polymer.
In the above production method, the obtained product may be washed with an aqueous sodium bicarbonate solution or the like. After washing, dehydration may be performed using sodium sulfate or the like.
In the step (s 1) and/or the step (s 2) of the above reaction, the difunctional phenol compound (a), the optional diamine compound (B), the optional (poly) oxyalkylene diamine compound (C), and the aldehyde compound (D) are preferably reacted while being heated in a solvent. In the step (s 3) of the above reaction, the monofunctional phenol compound (E) is preferably reacted with heating in a solvent.
[ 3. Composition ]
The following thermosetting composition can also be prepared and used: the thermosetting resin of the present invention is contained as a main component, and other thermosetting resins, thermoplastic resins, and compounding agents are contained as subcomponents.
Examples of the other thermosetting resin include epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, silicone resins, melamine resins, urea resins, allyl resins, phenolic resins, unsaturated polyester resins, bismaleimide resins, alkyd resins, furan resins, polyurethane resins, and aniline resins.
Examples of the thermoplastic resin include thermoplastic epoxy resin and thermoplastic polyimide resin.
Examples of the compounding agent include flame retardants, nucleating agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, slip agents, flame retardant aids, antistatic agents, opacifiers, fillers, softeners, plasticizers, colorants, and the like, as necessary. These may be used alone or in combination of 2 or more. Reactive or non-reactive solvents may also be used.
[4] Uncured molded article (molded article of thermosetting resin) and partially cured molded article ]
The thermosetting resin or the composition thereof of the present invention also has moldability before curing. Therefore, depending on the purpose and purpose, an uncured molded body in which the thermosetting resin or composition is molded in a non-cured manner, or a partially cured molded body in which only a part is cured instead of being completely cured may be used. The molding temperature (the highest temperature in the case of gradually increasing the temperature) is not particularly limited, but is preferably not less than room temperature and not more than 200 ℃, more preferably not less than 40 ℃ and not more than 180 ℃, still more preferably not less than 60 ℃ and not more than 160 ℃, and most preferably not less than 100 ℃ and not more than 160 ℃. If the molding temperature is less than 200 ℃, curing does not occur, and a desired uncured molded article can be obtained.
The dimensions and shapes of the uncured molded body and the partially cured molded body are not particularly limited, and examples thereof include films, sheets, plates, blocks, and the like, and may further include other portions (for example, an adhesive layer).
The uncured molded article and the partially cured molded article can be used as a precursor of a cured molded article described later, and can be used as an adhesive sheet having curability, for example.
From the viewpoint of the decomposition temperature, the uncured molded body and the partially cured molded body preferably have a small weight reduction ratio. The weight reduction ratio is a ratio of the weight reduction of the thermosetting resin after heating at a predetermined temperature for a predetermined time, assuming that the weight of the thermosetting resin before thermosetting is 100. The weight loss can be determined by thermogravimetric analysis (Thermogravimetric Anarysis: TGA). The weight reduction rate is preferably 5% or less, more preferably 3% or less. In addition, the smaller the weight reduction ratio, the more preferable, for example, the lower limit may be 0.01%. The weight reduction ratio may be measured, for example, at a temperature at which the thermoplastic processing of the uncured molded article is a prerequisite, or at a temperature at which the uncured molded article is cured, and the latter temperature is more preferable.
The uncured shaped body and the partially cured shaped body preferably have a relatively high decomposition onset temperature. The decomposition start temperature can be obtained from the TG inflection point using the TGA described above. The decomposition start temperature is preferably 250℃or higher, more preferably 255℃or higher. This can suppress the decomposition of the compound during curing of the uncured molded article.
From the viewpoint of excellent toughness and high elongation of the uncured molded body and the partially cured molded body, the glass transition temperature (Tg) of the uncured molded body is preferably 23 ℃ or less, more preferably 0 ℃ or less, and most preferably-10 ℃ or less. In addition, from the viewpoint of decomposition temperature at the time of curing, the glass transition temperature of the uncured molded body is preferably-150 ℃ or higher, more preferably-100 ℃ or higher, and preferably-60 ℃ or higher. If the glass transition temperature is within the above range, the uncured molded body exhibits excellent toughness and high elongation even in the vicinity of room temperature (25 ℃).
The mechanical properties of the uncured molded article and the partially cured molded article can be evaluated by, for example, tensile Modulus of elasticity (Modulus), tensile breaking strength, and tensile elongation at break. The respective characteristics can be measured by a known tensile tester. It can be said that the smaller the values of the tensile elastic modulus and tensile breaking strength are, the more excellent the softness is. On the other hand, it can be said that the larger the value of the tensile elongation at break, the more excellent the flexibility.
From the viewpoints of excellent toughness, high elongation, and flexibility of the uncured molded article, the tensile elastic modulus of the uncured molded article is preferably 10GPa or less, more preferably 5GPa or less, and most preferably 1GPa or less. In the case where n=1 or more, it is preferably 3GPa or less, more preferably 1GPa or less, and most preferably 0.1GPa or less. In addition, from the viewpoint of ease of handling of the uncured molded article, the tensile elastic modulus of the uncured molded article is preferably 0.00001GPa or more, more preferably 0.0001GPa or more, and most preferably 0.001GPa or more. In the case where n=1 or more, it is preferably 0.0001GPa or more, more preferably 0.005GPa or more, and most preferably 0.001GPa or more.
From the viewpoint of flexibility, the tensile breaking strength of the uncured molded article is preferably 500MPa or less, more preferably 100MPa or less, and most preferably 10MPa or less. From the viewpoints of ease of handling and fracture resistance of the uncured molded article and the partially cured molded article, the tensile fracture strength of the uncured molded article is preferably 0.01MPa or more, more preferably 0.1MPa or more, and most preferably 1MPa or more. In the case where n=1 or more, it is preferably 0.1MPa or more, more preferably 1MPa or more, and most preferably 1.5MPa or more.
From the viewpoints of the excellent toughness and the degree of high elongation of the uncured molded body and the partially cured molded body, the tensile elongation at break of the uncured molded body is preferably 10% or more, more preferably 50% or more, and most preferably 100% or more. In the case where n=1 or more, it is preferably 3% or more, more preferably 10% or more, and most preferably 80% or more.
The tensile elongation at break of the uncured molded article and the partially cured molded article is preferably 1 or more times, preferably 1.5 or more times the tensile elongation at break of the cured molded article described later. The uncured molded article has a tensile elongation at break of 1 time or more that of the cured molded article, and has toughness and high elongation superior to those of the cured molded article.
The uncured molded body and the partially cured molded body can be deformed into arbitrary shapes by having excellent toughness. For example, an uncured film having excellent toughness does not exhibit cracking, or the like even if agglomerated or deformed into an arbitrary shape.
The uncured molded article and the partially cured molded article preferably have both thermoplastic reshaping properties and toughness at the time of reshaping. Thermoplastic reshaping means: for example, after the uncured molded body and the partially cured molded body are deformed into arbitrary shapes, the uncured molded body and the partially cured molded body can be restored to the shapes before deformation when heated at a temperature at which the uncured molded body and the partially cured molded body are not completely cured. The temperature at which the uncured molded body and the partially cured molded body are not completely cured is 200 ℃ or less. The toughness at the time of reforming means: when the heating is performed at a temperature at which the uncured molded body and the partially cured molded body are not completely cured, cracking or crazing does not occur, as compared with the case before and after the heating. In addition, even if the uncured molded body and the partially cured molded body are subjected to deformation and heat reforming for 1 or more times, the reforming property and toughness can be maintained. In this specification, this property is referred to as "repeated thermoplasticity". Thus, the uncured molded body is easier to handle, and the range of use of the uncured molded body is wider.
An uncured shaped body refers to a shaped body having a degree of cure of less than 1%. For example, the degree of cure of the uncured resin that is not heated at all may be set to 0%, while the degree of cure of the cured molded article that is sufficiently heat-treated and has been confirmed by DSC, for example, that the peak corresponding to curing has disappeared may be set to 100%. The degree of cure of the uncured molded article can be calculated from the ratio of the area of the curing exothermic peak of the uncured resin obtained by DSC to the area of the curing exothermic peak of the uncured molded article.
The degree of solidification of the partially cured molded article is 1% or more and 99% or less, and preferably 1% or more and less than 90% from the viewpoint of repeated thermoplasticity. When the curing degree is less than 1%, thermoplastic formability is good, but toughness at the time of reforming may be insufficient. In addition, when the degree of cure is more than 99%, thermoplastic reshaping may be insufficient. Among them, if thermoplastic reshaping is important depending on the use of the partially cured molded article or the required processing method, it is preferable to use a partially cured molded article having a lower degree of curing. If importance is attached to toughness at the time of reshaping, it is preferable to use a partially cured molded article having a higher degree of curing. The degree of curing of the partially cured molded article can be calculated from the ratio of the area of the curing exothermic peak of the uncured resin obtained by DSC to the area of the curing exothermic peak of the partially cured molded article.
The degree of solidification of the partially cured molded article is more preferably 2% or more and 80% or less, still more preferably 2% or more and 70% or less, still more preferably 2% or more and 60% or less, still more preferably 3% or more and 40% or less, and most preferably 3% or more and 30% or less.
In addition, the uncured molded body and the partially cured molded body preferably have flexibility. Softness can be evaluated, for example, by a spindle test based on JIS K-5600-5-1:1999. In the mandrel test, the smaller the bending radius of the material, the higher the softness can be evaluated. The bending radius as evaluated by the mandrel test is preferably 2mm or less, and more preferably 1mm or less. Thus, the uncured molded body and the partially cured molded body have flexibility capable of withstanding 180 ° bending.
[ 5] Cured molded article (molded article of cured product) ]
The molded article (uncured molded article) of the thermosetting resin or the partially cured molded article is cured by applying heat thereto, whereby a cured molded article can be obtained. The thermosetting resin or the composition thereof of the present invention is molded and cured by applying heat at the same time so as not to undergo molding treatment of an uncured molded article or a partially cured molded article, whereby a cured molded article can be obtained. The curing temperature (the highest temperature in the case of gradual temperature rise) is not particularly limited, but is preferably 200 ℃ or higher and 300 ℃ or lower, more preferably 210 ℃ or higher and 280 ℃ or lower, still more preferably 220 ℃ or higher and 260 ℃ or lower, and most preferably 240 ℃ or higher and 260 ℃ or lower. If the curing temperature is 200℃or higher, a molded article having sufficient curing can be obtained. In addition, if the curing temperature is less than 300 ℃, thermal decomposition does not occur, and a desired cured molded article can be obtained. The cured molded article of the present invention is a cured molded article having a degree of cure of more than 99%.
In the case where n=1 or more, the glass transition temperature (Tg) of the cured molded article is preferably 300 ℃ or less, more preferably 250 ℃ or less, and most preferably 200 ℃ or less, from the viewpoints of excellent toughness and high elongation of the cured molded article. In the case where n=0, the upper limit of Tg is not limited. Further, from the viewpoint of the decomposition temperature, the glass transition temperature of the cured molded article is preferably-150℃or higher, more preferably-100℃or higher, and still more preferably-60℃or higher. If the glass transition temperature is within the above range, the cured molded body exhibits excellent toughness and high elongation even in the vicinity of room temperature (25 ℃). When n=0, the glass transition temperature of the cured molded article is preferably 100 ℃ or higher, more preferably 150 ℃ or higher. When n=0, the glass transition temperature of the cured molded article may be 200 ℃ or higher. If the glass transition temperature is within the above range, the cured molding exhibits excellent heat resistance.
The thermal decomposition temperature (Td 5) of the cured molded body refers to the corresponding temperature when the weight of the compound is reduced by 5% by thermal decomposition, measured in an environment where the uncured molded body is cured. From the viewpoint of making the cured molded body less susceptible to thermal decomposition, the thermal decomposition temperature (Td 5) is preferably 200 ℃ or higher, more preferably 230 ℃ or higher, and most preferably 250 ℃ or higher.
From the viewpoint of the excellent toughness and the degree of high elongation of the cured molded body, the tensile elastic modulus of the cured molded body is preferably 10GPa or less, more preferably 5GPa or less, and most preferably 3GPa or less. When n=1 or more, the tensile elastic modulus of the cured molded article is preferably 2GPa or less. In addition, from the viewpoint of ease of handling of the cured molded article, the tensile elastic modulus of the cured molded article is preferably 0.0001GPa or more, more preferably 0.0005GPa or more, and most preferably 0.001GPa or more. When n=0, it is preferably 0.1GPa or more, more preferably 0.5GPa or more, and most preferably 1GPa or more.
From the viewpoint of making the cured molded body hard to fracture, the tensile fracture strength of the cured molded body is preferably 0.1MPa or more, more preferably 1MPa or more, and most preferably 1.5MPa or more. In the case where n=0, the tensile breaking strength of the cured molded product is preferably 5MPa or more, more preferably 10MPa or more, and most preferably 50MPa or more from the viewpoint of toughness.
In addition, from the viewpoint of ease of handling of the cured molded body, the tensile breaking strength of the cured molded body is preferably 1000MPa or less, more preferably 500MPa or less, and most preferably 100MPa or less.
From the viewpoint of toughness, the tensile elongation at break of the cured molded article is preferably 0.1% or more, more preferably 1% or more, still more preferably 3% or more, and most preferably 5% or more. In the case where n=1 or more, the tensile elongation at break of the cured molded article is preferably 3% or more, more preferably 4% or more, and most preferably 5% or more, from the viewpoint of the excellent toughness and the high elongation of the cured molded article.
The cured molded article preferably has flexibility similar to the uncured molded article and the partially cured molded article. Softness can be evaluated, for example, by a spindle test based on JIS K-5600-5-1:1999. The bending radius as evaluated by the mandrel test is preferably 2mm or less. Thus, the cured molded article has flexibility capable of withstanding 180 ° bending.
The size and shape of the cured molded article are not particularly limited, and examples thereof include films, sheets, plates, blocks, and the like, and may further include other portions (for example, an adhesive layer).
The cured molded article can be suitably used for applications such as electronic parts and electronic devices, and materials thereof, particularly multilayer substrates, laminated boards, sealants, adhesives, and the like, which require excellent dielectric characteristics, and also for applications such as aircraft parts, automobile parts, and building parts. The cured molded article of the present invention is particularly preferably applicable to the production of semi-prepregs, and carbon fiber composite materials.
The cured molded article may contain reinforcing fibers from the viewpoint of improving the mechanical strength of the cured molded article. Examples of the reinforcing fibers include inorganic fibers, organic fibers, metal fibers, and reinforcing fibers having a mixed structure obtained by combining them. The number of reinforcing fibers may be 1 or 2 or more.
Examples of the inorganic fibers include carbon fibers, graphite fibers, silicon carbide fibers, alumina fibers, tungsten carbide fibers, boron fibers, and glass fibers. Examples of the organic fibers include aramid fibers, high-density polyethylene fibers, other general nylon fibers, and polyester fibers. The metal fibers include fibers such as stainless steel and iron. Further, as the metal fiber, a carbon-coated metal fiber in which a metal fiber is coated with carbon is exemplified. Among them, the reinforcing fiber is preferably carbon fiber from the viewpoint of improving the strength of the cured product.
In general, the carbon fibers are subjected to sizing treatment, but may be used as they are, and if necessary, the sizing agent may be removed by using a fiber having a small amount of sizing agent, or by a conventional method such as an organic solvent treatment or a heat treatment. In addition, the carbon fiber bundles may be opened by using air, a roller, or the like in advance, and the resin may be easily impregnated between the carbon fiber filaments. By reducing the amount of the sizing agent used or removing the sizing agent, voids and discoloration of the resin caused by decomposition of the sizing agent at high temperature can be suppressed.
One embodiment of the present invention also includes a prepreg or semi-prepreg obtained by impregnating the reinforcing fiber with the thermosetting resin or composition of the present invention. In the present specification, the semi-prepreg means an integrated composite obtained by locally impregnating reinforcing fibers (semi-impregnated state) with a thermosetting resin or composition.
In addition, prepregs may be obtained from the semi-prepregs described above. For example, the semi-prepreg may be further melted by heating to impregnate the reinforcing fibers with the resin, thereby obtaining a prepreg. That is, in the present specification, the prepreg may be said to be formed by impregnating reinforcing fibers with a resin to a greater extent than the semi-prepreg.
[ 6. Carbon fiber composite ]
The cured molded article of the present invention can be used as a carbon fiber composite material. Carbon fiber composites are also known as Carbon Fiber Reinforced Plastics (CFRP). The method for producing the carbon fiber composite material is not particularly limited, and for example, the following method can be employed: impregnating carbon fibers with a resin to obtain a sheet, and using the sheet as a semi-prepreg or a prepreg; or impregnating carbon fibers (in the form of bundles or fabrics) with a liquid resin. The cured molded article of the present invention may be molded into a semi-prepreg or a prepreg, and the semi-prepreg or the prepreg may be used for producing a carbon fiber composite material.
Although carbon fiber composites are exemplified here as an example, the reinforcing fibers that can be used are not limited to carbon fibers as described above. That is, in one embodiment of the present invention, the following fiber composite is further included: a fiber composite material obtained by impregnating a reinforcing fiber with the thermosetting resin or the composition of the present invention and curing the thermosetting resin or the composition.
The semi-prepregs or prepregs can be obtained, for example, by the following methods: the sheet (carbon fiber plain-weave material) is obtained by impregnating carbon fibers with a resin, and the cured molded product of the present invention is laminated on the front and back surfaces of the sheet and pressed at a predetermined temperature and a predetermined pressure.
In addition to carbon fibers, the semi-prepreg or prepreg may be a reinforcing fiber described in the column [ 5. Cured molded article (molded article of cured product) ].
The carbon fiber composite material can be manufactured by the following method: a plurality of semi-prepregs or prepregs are laminated and pressed at a predetermined temperature and a predetermined pressure. By such pressing, voids mainly formed between carbon fibers can be suppressed. In addition, pressing under vacuum conditions (vacuum pressing) is more preferable. By vacuum pressing, formation of voids between resins can also be suppressed. In addition, the vacuum pressing can increase the temperature rising rate as compared with the usual pressing. Or after the usual pressing, heating using a vacuum oven is performed, and the formation of voids between the resins can be suppressed as well.
The pressure is preferably 1 to 5MPa, more preferably 1 to 3MPa. The temperature is preferably 50℃or higher, more preferably 100℃or higher. The temperature is preferably 400℃or lower, more preferably 300℃or lower.
The pressure and temperature may be increased stepwise. For example, a method of manufacturing a carbon fiber composite material may include: (1) A step of treating the mixture at 50 to 200 ℃ for 5 to 20 minutes under atmospheric pressure; (2) Treating at 50-200 deg.c under 1-5 MPa for 10-30 min; (3) And treating at a temperature of 1 to 5MPa, more than 200 ℃ and less than 400 ℃ for 1 to 5 hours.
In addition, if the temperature is raised during the pressing, it is preferable to raise the temperature so that the material is not taken out of the press. This can further suppress the formation of voids between the carbon fibers.
The laminated semi-prepreg or prepreg may be covered with a release film. Examples of the release film include Polyimide (PI) films. By such coating, the amount of resin oozing out of the carbon fiber composite material can be reduced.
[ 7. Summary ]
One embodiment of the present invention may include the following.
< 1 > A thermosetting resin having a benzoxazine ring structure as shown in the general formula (I) in its main chain.
[ In the general formula (I),
Ar 1 and Ar 2 each represent a 4-valent aromatic group derived from the difunctional phenol compound (A), ar 1 and Ar 2 may be the same or different groups from each other,
N represents an integer of 0 or more,
When n=0, R 1 represents a linear alkylene group having 8 to 12 carbon atoms derived from the aliphatic diamine compound (B), and when n=1 or more, R 1 represents a linear alkylene group having 6 to 12 carbon atoms derived from the aliphatic diamine compound (B),
R 2 represents a (poly) oxyalkylene group derived from a (poly) oxyalkylene diamine compound (C),
In the case where n=0, at least one of the 2 terminals of the main chain is a group represented by the following general formula (II) derived from the monofunctional phenol compound (E), and the 2 terminals may be the same or different groups from each other,
N=0, m represents an integer of 2 or more, n=1 or more, m represents an integer of 1 or more,
The repeating units represented by m and the repeating units represented by n are repeated in a random manner, or in a block manner, or are alternately copolymerized. A kind of electronic device
[ In the general formula (II),
X represents a hydrogen atom or an organic group having 1 to 20 carbon atoms,
L represents an integer of 0 to 3. A kind of electronic device
< 2 > The thermosetting resin according to < 1 >, wherein, the difunctional phenol compound (A) is selected from the group consisting of 2, 2-bis (4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2-bis (4-hydroxyphenyl) hexafluoropropane, 2-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) diphenylmethane, 2-bis (3-methyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) -2, 2-dichloroethylene, 1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane at least one difunctional phenol compound of 2, 2-bis (4-hydroxy-3-isopropylphenyl) propane, 1, 3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, bis (4-hydroxyphenyl) sulfone, 1, 4-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 5'- (1-methylethylene) -bis [1,1' - (bisphenyl) -2-ol ] propane, 1-bis (4-hydroxyphenyl) -3, 5-trimethylcyclohexane, 1-bis (4-hydroxyphenyl) cyclohexane.
< 3 > The thermosetting resin according to < 1 > or < 2 >, wherein the (poly) oxyalkylene diamine compound (C) has a (poly) oxyethylene group, and/or a (poly) oxypropylene group.
The thermosetting resin according to any one of < 1 > - < 3 >, wherein the ratio of m to n in the general formula (I) is: n/m=1/0.1 to 1/100.
A composition comprising the thermosetting resin of any one of < 1 > - < 4 >.
< 6 > An uncured molded article obtained by molding the thermosetting resin according to any one of < 1 > - < 4 >.
The uncured molded article of < 7 > according to < 6 >, wherein the radius of curvature of the uncured molded article is 2mm or less under a mandrel test conducted in accordance with JIS K-5600-5-1:1999.
A partially cured molded article obtained by partially curing the thermosetting resin of any one of < 1 > - < 4 > and having a degree of curing of 1 to 99%.
The partially cured molded article of < 9 > according to < 8 >, wherein the bending radius of the partially cured molded article is 2mm or less under a mandrel test according to JIS K-5600-5-1:1999.
A cured molded article obtained by curing the thermosetting resin according to any one of < 1 > - < 4 >.
The cured molded article of < 11 > according to < 10 >, wherein the cured molded article has a bending radius of 2mm or less under a mandrel test according to JIS K-5600-5-1:1999.
< 12 > A thermosetting resin having a benzoxazine ring structure in its main chain, wherein,
An uncured molded article obtained by molding the thermosetting resin and having a degree of cure of less than 1%, or a partially cured molded article obtained by curing the thermosetting resin and having a degree of cure of 1 to 99%, has thermoplastic reshaping properties and toughness,
The thermoplastic reshaping properties refer to the following properties: the uncured molded body or the partially cured molded body is deformed into an arbitrary shape and then returns to a shape before deformation when heated at 200 ℃ or less,
The toughness refers to the following properties: compared with the heating before and after, the uncured shaped body or the partially cured shaped body does not generate cracks or fissures,
The thermosetting resin has a repeating thermoplastic, which means: the reshaping property and the toughness can be maintained even if subjected to the deformation and the heating more than 1 time.
< 13 > A method for producing a thermosetting resin, wherein the main chain of the thermosetting resin has a benzoxazine ring structure,
The method for producing the thermosetting resin comprises the following steps:
step (s 1) of reacting a difunctional phenol compound (a), an aliphatic diamine compound (B) and an aldehyde compound (D);
An optional step (s 2) of reacting the difunctional phenol compound (A), (poly) oxyalkylene diamine compound (C) and aldehyde compound (D);
An optional step (s 3) of reacting the monofunctional phenol compound (E),
And
In the case where step (s 2) is not included, the manufacturing method includes step (s 3),
In the case where step (s 2) is included, the aliphatic diamine compound (B) is an aliphatic diamine having a linear alkylene group having 6 to 12 carbon atoms, in the case where step (s 2) is not included, the aliphatic diamine compound (B) is an aliphatic diamine having a linear alkylene group having 8 to 12 carbon atoms,
The (poly) oxyalkylene diamine compound (C) has a (poly) oxyethylene group and/or a (poly) oxypropylene group.
A method for producing a thermosetting resin according to < 14 > and < 13 >, wherein,
The molar ratio of the aliphatic diamine compound (B) to the (poly) oxyalkylene diamine compound (C) is: (poly) oxyalkylene diamine compound (C)/aliphatic diamine compound (B) =1/0.1 to 1/100.
In addition, other embodiments of the present invention may include the following.
< A1 > a thermosetting resin having a benzoxazine ring structure as shown in the general formula (I) in its main chain.
In the formula (I) of the formula (I),
Ar 1 and Ar 2 each represent a 4-valent aromatic group derived from the difunctional phenol compound (A), ar 1 and Ar 2 may be the same or different groups from each other,
R 1 represents a linear alkylene group having 6 to 12 carbon atoms derived from the aliphatic diamine compound (B),
R 2 represents a (poly) oxyalkylene group derived from a (poly) oxyalkylene diamine compound (C),
M represents an integer of 1 or more,
N represents an integer of 1 or more,
The repeating units represented by m and the repeating units represented by n are repeated in a random manner, or in a block manner, or are alternately copolymerized. A kind of electronic device
< A2 > the thermosetting resin according to < A1 >, wherein,
The difunctional phenol compound (A) is selected from the group consisting of 2, 2-bis (4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2-bis (4-hydroxyphenyl) hexafluoropropane, 2-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) diphenylmethane, 2-bis (3-methyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) -2, 2-dichloroethylene, 1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane at least one difunctional phenol compound of 2, 2-bis (4-hydroxy-3-isopropylphenyl) propane, 1, 3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, bis (4-hydroxyphenyl) sulfone, 1, 4-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 5'- (1-methylethylene) -bis [1,1' - (bisphenyl) -2-ol ] propane, 1-bis (4-hydroxyphenyl) -3, 5-trimethylcyclohexane, 1-bis (4-hydroxyphenyl) cyclohexane.
< A3 > the thermosetting resin according to < A1 > or < A2 >, wherein the (poly) oxyalkylene diamine compound (C) has a (poly) oxyethylene group and/or a (poly) oxypropylene group.
The thermosetting resin according to any one of < A1 > - < A3 >, wherein in the formula (I), the ratio of m to n is: n/m=1/0.1 to 1/100.
A5 > a composition comprising the thermosetting resin of any one of A1 to A4.
An uncured molded article obtained by molding the thermosetting resin of any one of < A1 > - < A4 > or the composition of < A5 >.
< A7 > the uncured molded article according to < A6 >, wherein the radius of curvature of the uncured molded article is 2mm or less under a mandrel test conducted in accordance with JIS K-5600-5-1:1999.
A8 is a partially cured molded article obtained by partially curing the thermosetting resin of any one of A1 to A4, the composition of A5 or the uncured molded article of A6, and the degree of curing is 1 to 99%.
< A9 > the partially cured molded article according to < A8 >, wherein the bending radius of the partially cured molded article is 2mm or less under a mandrel test conducted in accordance with JIS K-5600-5-1:1999.
A10 is a cured molded article obtained by curing the thermosetting resin of any one of A1 to A4, the composition of A5, the uncured molded article of A6, or the partially cured molded article of A8.
A11 > the cured molded article according to A10, wherein the bending radius of the cured molded article is 2mm or less under a mandrel test according to JIS K-5600-5-1:1999.
< A12 > a thermosetting resin having a benzoxazine ring structure in its main chain, wherein,
An uncured molded article obtained by molding the thermosetting resin and having a degree of cure of less than 1%, or a partially cured molded article obtained by curing the thermosetting resin and having a degree of cure of 1 to 99%, has thermoplastic reshaping properties and toughness,
The thermoplastic reshaping properties refer to the following properties: the uncured molded body or the partially cured molded body is deformed into an arbitrary shape and then returns to a shape before deformation when heated at 200 ℃ or less,
The toughness refers to the following properties: compared with the heating before and after, the uncured shaped body or the partially cured shaped body does not generate cracks or fissures,
The thermosetting resin has a repeating thermoplastic, which means: the reshaping property and the toughness can be maintained even if subjected to the deformation and the heating more than 1 time.
< A13 > a method for producing a thermosetting resin,
Wherein the main chain of the thermosetting resin has a benzoxazine ring structure,
The method for producing the thermosetting resin comprises the following steps:
Step (s 1) of reacting a difunctional phenol compound (a), an aliphatic diamine compound (B) and an aldehyde compound (D); and
Step (s 2) of reacting the difunctional phenol compound (A), (poly) oxyalkylene diamine compound (C) and aldehyde compound (D),
The aliphatic diamine compound (B) is an aliphatic diamine having a linear alkylene group having 6 to 12 carbon atoms,
The (poly) oxyalkylene diamine compound (C) has a (poly) oxyethylene group and/or a (poly) oxypropylene group.
< A14 > the method for producing a thermosetting resin according to < A13 >, wherein,
The molar ratio of the aliphatic diamine compound (B) to the (poly) oxyalkylene diamine compound (C) is: (poly) oxyalkylene diamine compound (C)/aliphatic diamine compound (B) =1/0.1 to 1/100.
A15 is a prepreg or semi-prepreg obtained by impregnating reinforcing fibers with the thermosetting resin described in any one of A1 to A4 or with the composition described in A5.
< A16 > a fiber composite material comprising a reinforcing fiber impregnated with the thermosetting resin of any one of < A1> to < A4> or the composition of < A5> and cured.
Other embodiments of the invention may include the following.
< B1 > a thermosetting resin having a benzoxazine ring structure as shown in the general formula (I') in its main chain.
In the formula (I '), the amino acid sequence of the formula (I'),
Ar 1 represents a 4-valent aromatic group derived from a difunctional phenol compound (A),
R 1 represents a linear alkylene group having 8 to 10 carbon atoms derived from the aliphatic diamine compound (B),
At least one of A and B is a group derived from a monofunctional phenol compound (E) and represented by the following general formula (II), A and B may be the same or different,
M represents an integer of 2 or more. A kind of electronic device
[ In the formula (II),
X represents a hydrogen atom or an organic group having 1 to 20 carbon atoms,
L represents an integer of 0 to 3. A kind of electronic device
< B2 > a composition comprising the thermosetting resin described as < B1 >.
< B3 > an uncured molded article obtained by molding the thermosetting resin described as < B1 > or the composition described as < B2 >.
< B4 > a cured molded article obtained by curing the thermosetting resin < B1 >, the composition < B2 > or the uncured molded article < B3 >.
< B5 > a method for producing a thermosetting resin, wherein the main chain of the thermosetting resin has a benzoxazine ring structure,
The method for producing the thermosetting resin comprises the following steps:
Step (s 1) of reacting a difunctional phenol compound (a), an aliphatic diamine compound (B) and an aldehyde compound (D); and
A step (s 3) of reacting the monofunctional phenol compound (E),
The aliphatic diamine compound (B) is an aliphatic diamine having a linear alkylene group having 8 to 10 carbon atoms.
Other embodiments of the invention may include the following.
< C1 > a thermosetting resin having a benzoxazine ring structure as shown in the general formula (I') in its main chain.
In the formula (I '), the amino acid sequence of the formula (I'),
Ar 1 represents a 4-valent aromatic group derived from a difunctional phenol compound (A),
R 1 represents a linear alkylene group having 12 carbon atoms derived from the aliphatic diamine compound (B),
At least one of A and B is a group represented by the following general formula (II) derived from a monofunctional phenol compound (E), A and B may be the same or different,
M represents an integer of 2 or more. A kind of electronic device
[ In the formula (II),
X represents a hydrogen atom or an organic group having 1 to 20 carbon atoms,
L represents an integer of 0 to 3. A kind of electronic device
< C2 > a composition comprising a thermosetting resin as described in < C1 >.
< C3 > an uncured molded article obtained by molding the thermosetting resin described as < C1 > or the composition described as < C2 >.
A cured molded article of < C4 > which is obtained by curing the thermosetting resin of < C1 >, the composition of < C2 > or the uncured molded article of < C3 >.
< C5 > a method for producing a thermosetting resin, wherein the main chain of the thermosetting resin has a benzoxazine ring structure,
The method for producing the thermosetting resin comprises the following steps:
Step (s 1) of reacting a difunctional phenol compound (a), an aliphatic diamine compound (B) and an aldehyde compound (D); and
A step (s 3) of reacting the monofunctional phenol compound (E),
The aliphatic diamine compound (B) is an aliphatic diamine having a linear alkylene group having 12 carbon atoms.
The present invention is not limited to the above embodiments, and various modifications may be made within the scope of the description, and embodiments in which the technical means disclosed in the respective embodiments are appropriately combined are also included in the technical scope of the present invention.
Examples
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
[ Test method ]
The compounds obtained in the following examples and comparative examples were tested for molecular weight, minimum melt viscosity, weight reduction (%), decomposition start temperature (. Degree.C.), glass transition temperature (Tg), thermal decomposition temperature (Td 5), tensile elastic modulus, tensile breaking strength and tensile elongation at break by the following methods.
(1) Determination of molecular weight
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated in terms of standard polystyrene using a gel permeation chromatograph (GPC, shimadzu corporation).
(2) Determination of minimum melt viscosity
The measurement was performed using ARES G2 (manufactured by TA Instruments Co., ltd.) with 25mm parallel plates at a heating rate of 5℃per minute, an angular frequency of 10.0rad/s (1.6 Hz), and a deformation rate of 0.01%. The minimum melt viscosity is the lowest value of the melt viscosity measured under such conditions.
(3) Weight reduction ratio (%), decomposition initiation temperature (. Degree.C.)
The uncured resin was evaluated for weight loss by thermogravimetric analysis (TGA) using a thermogravimetric analysis apparatus (STA 7200, manufactured by hitachi high tech), under a condition of a temperature rise rate of 5 ℃/min. The weight reduction (%) was obtained from the weight at room temperature before the start of measurement and the weight after curing under the curing conditions. The decomposition start temperature was also obtained from the TG inflection point temperature.
(4) Glass transition temperature (Tg)
The uncured film and the cured film were measured using a dynamic viscoelasticity measuring apparatus (DVA-200, manufactured by IT measurement control Co., ltd.) under the conditions of a frequency (1 Hz) and a heating rate of 5 ℃/min, and a DMA curve was obtained. The temperature at the intersection point where the tangent line of the inflection point of the storage elastic modulus (E') on the obtained DMA curve intersects with the base line was taken as Tg.
(5) Thermal decomposition temperature (Td 5)
The uncured film and the cured film were evaluated for a 5% weight loss temperature (Td 5) by thermogravimetric analysis (TGA) using a thermogravimetric differential thermal analysis apparatus (STA 7200, manufactured by hitachi high tech) at a temperature rise rate of 5 ℃/min. Here, the differential thermal analysis (TG-DTA) value measured under an N 2 gas flow was used as Td5.
(6) Modulus of elasticity in tension (Modulus), tensile breaking strength and tensile elongation at break
The uncured film (film-like uncured product) and the cured film (cured product) were subjected to a tensile test using a tensile tester (EZ-SX, manufactured by Shimadzu corporation). The test temperature was room temperature, the stretching speed was 5mm/min, and the test piece was 50mm in length and 3mm in width.
(7) Thermoplastic (toughness at reshaping, thermoplastic reshaping)
For the uncured film and the partially cured film, thermoplasticity (toughness at the time of reforming, thermoplastic reforming) was evaluated visually. The toughness was evaluated by visually evaluating whether or not there were cracks, flaws, and the like of the film when the film was deformed by hand before and after heating, respectively. After the deformed film was heated at a predetermined temperature for a predetermined time without causing the film to be completely cured, the re-formability was evaluated according to whether the film was restored to the state before deformation.
(Toughness evaluation criterion)
O: no cracking or cracking was observed on the film.
X: cracks or fissures were observed on the film.
(Evaluation criterion for reshaping Property)
O: the membrane returns to its pre-deformed state.
X: the film remains deformed or does not recover to its pre-deformed state.
(8) Softness evaluation (mandrel test)
For the partially cured film and the cured film, softness evaluation was performed by a spindle test based on JIS K-5600-5-1:1999. In which a cylindrical mandrel measuring device Elcometer 1500 was used. The film was hung on a plurality of cylindrical spindles (2 mm to 32 mm) having different diameters, and both ends of the film were stretched. That is, in a state where the film is bent along the curved surface of the cylindrical mandrel, both ends of the film are stretched in a direction perpendicular to the long axis direction of the cylindrical mandrel. The diameter of the smallest cylinder mandrel among these cylinder mandrels which did not break after stretching was taken as the bending radius (mm) of the film.
< Production of resin >
The materials used in the production of the resin are as follows.
[ Difunctional phenol Compound (A) ]
2, 2-Bis (4-hydroxyphenyl) propane (bisphenol A, bisA, manufactured by Tokyo Chemical Industry (TCI)) Co., ltd
[ Aliphatic diamine Compound (B) ]
Hexamethylenediamine (HMD, manufactured by Tokyo Chemical Industry (TCI), co., ltd.)
Octamethylenediamine (manufactured by Tokyo Chemical Industry (TCI)) company
Decamethylenediamine (manufactured by Tokyo Chemical Industry (TCI)) company
Dodecyl methylene diamine (manufactured by Tokyo Chemical Industry (TCI)) company
[ Poly ] oxyalkylene diamine compound (C) ]
Jeffamine D2000 (Hentsman company)
[ Aldehyde Compound (D) ]
Paraformaldehyde (manufactured by Merck Co., ltd.)
[ Monofunctional phenol Compound (E) ]
Phenol (manufactured by Tokyo Chemical Industry (TCI)) Co., ltd
[ Example 1 (C8 Bz) ]
A benzoxazine-based thermosetting resin (C8 Bz) having a structural unit derived from C8 diamine (i.e., octamethylenediamine) was obtained by the method shown below.
To chloroform (30 mL) was added 3.1961g (0.014 mol) of bisphenol A, 3.1654g (0.020 mol) of octamethylenediamine, 2.5832g (0.086 mol) of paraformaldehyde, 1.1316g (0.012 mol) of phenol, and these were reacted at 60 ℃. After 4 hours the reaction was stopped. After the reaction solution was cooled to room temperature, 3 times of separation was performed using 60mL of a 0.1N sodium bicarbonate solution. The reaction solution washed with sodium sulfate was dehydrated and filtered. The solvent was removed under heating and reduced pressure with an evaporator, and dried under reduced pressure at 40 ℃ with a vacuum oven, whereby a powder of the benzoxazine resin as the target compound was obtained. When the molecular weight was measured by GPC, the number average molecular weight (Mn) was 1552 and the weight average molecular weight (Mw) was 4404 in terms of standard polystyrene.
The powder of the benzoxazine resin obtained was heated at 100 ℃ for 30 minutes using a hot press to obtain a film-like uncured product. Further, it was heat-cured in an oven at 200℃for 1 hour, at 240℃for 1 hour, and at 260℃for 30 minutes to obtain a film-shaped cured product. The properties of the film-like uncured product and cured product are shown in table 1.
[ Example 2 (C10 Bz) ]
A benzoxazine-based thermosetting resin (C10 Bz) having a structural unit derived from C10 diamine (i.e., decamethylenediamine) was obtained by the method shown below.
To chloroform (40 mL) was added 6.3920g (0.028 mol) of bisphenol A, 6.9328g (0.040 mol) of decamethylenediamine, 5.1654g (0.172 mol) of paraformaldehyde, 2.2586g (0.024 mol) of phenol, and these were reacted at 60 ℃. After 4 hours, the reaction was stopped. After the reaction solution was cooled to room temperature, 3 times of separation was performed with 80mL of a 0.1N sodium bicarbonate solution. The reaction solution washed with sodium sulfate was dehydrated and filtered. The solvent was removed under heating and reduced pressure with an evaporator, and dried under reduced pressure at 40 ℃ with a vacuum oven, whereby a powder of the benzoxazine resin as the target compound was obtained. When the molecular weight was measured by GPC, the number average molecular weight (Mn) was 2097 and the weight average molecular weight (Mw) was 4582 in terms of standard polystyrene.
The powder of the benzoxazine resin obtained was heated at 100 ℃ for 30 minutes using a hot press to obtain a film-like uncured product. Further, it was heat-cured in an oven at 200℃for 1 hour, at 240℃for 1 hour, and at 260℃for 30 minutes to obtain a film-shaped cured product. The properties of the film-like uncured product and cured product are shown in table 1.
[ Example 3 (C12 Bz) ]
A benzoxazine-based thermosetting resin (C12 Bz) having a structural unit derived from C12 diamine (i.e., dodecylenediamine) was obtained by the method shown below.
To a mixed solvent of toluene (57.96 mL) and isobutanol (10.23 mL), 6.2324g (0.027 mol) of bisphenol A, 6.0012g (0.030 mol) of dodecylenediamine, 5.4051g (0.180 mol) of paraformaldehyde and 0.7678g (0.008 mol) of phenol were added, and reacted at 100 ℃. After 4 hours, the reaction was stopped. After the reaction mixture was cooled to room temperature, it was separated 4 times with 500mL of a 0.03N aqueous sodium hydroxide solution. The reaction solution washed with sodium sulfate was dehydrated and filtered. The solvent was removed under heating and reduced pressure with an evaporator, and dried under reduced pressure at 60 ℃ with a vacuum oven, whereby a powder of the benzoxazine resin as the target compound was obtained. When the molecular weight was measured by GPC, the number average molecular weight (Mn) was 2831 and the weight average molecular weight (Mw) was 5509, as calculated on the basis of standard polystyrene.
The powder of the benzoxazine resin obtained was heated at 100 ℃ for 30 minutes using a hot press to obtain a film-like uncured product. Further, it was heat-cured in an oven at 200℃for 1 hour, at 240℃for 1 hour, and at 260℃for 30 minutes to obtain a film-shaped cured product. The properties of the film-like uncured product and cured product are shown in table 1.
[ Example 4 (JD 11) ]
Bisphenol A (4.5669 g,0.02 mol), hexamethylenediamine (1.1631 g,0.01 mol), jeffamine D2000 (20.0191 g,0.01 mol), paraformaldehyde (2.5868 g,0.086 mol) were added to chloroform (40 mL) and reacted at 60 ℃. After 5 hours, the reaction was stopped. After the reaction solution was cooled to room temperature, 3 times of separation was performed using 60mL of a 0.1N sodium bicarbonate solution. The reaction solution washed with sodium sulfate was dehydrated and filtered. The solvent was removed under heating and reduced pressure with an evaporator, and dried under reduced pressure at 40 ℃ with a vacuum oven, whereby a powder of the benzoxazine resin as the target compound was obtained. When the molecular weight was measured by GPC, the number average molecular weight (Mn) was 6061 and the weight average molecular weight (Mw) was 17568 in terms of standard polystyrene.
The powder of the benzoxazine resin was heated and pressurized at 160℃under 10MPa for 30 minutes using a hot press to obtain a film-like uncured molded body (uncured film). The obtained uncured film was heat-cured at 210℃for 2 hours in a convection oven to obtain a cured molded article (cured film) in the form of a film. The properties of the uncured film and the cured film are shown in table 1. In addition, since jeffamine d2000 and hexamethylenediamine are used in a molar ratio of 1:1, the benzoxazine resin obtained in example 4 is also referred to as JD11.
[ Example 5 (JD 13) ]
Bisphenol A (4.5665 g,0.02 mol), hexamethylenediamine (1.7444 g,0.015 mol), jeffamine D2000 (10.0161 g,0.005 mol), paraformaldehyde (2.5857 g,0.086 mol) were added to chloroform (40 mL) and reacted at 60 ℃. After 5 hours, the reaction was stopped. After the reaction solution was cooled to room temperature, 3 times of separation was performed using 60mL of a 0.1N sodium bicarbonate solution. The reaction solution washed with sodium sulfate was dehydrated and filtered. The solvent was removed under heating and reduced pressure with an evaporator, and dried under reduced pressure at 40 ℃ with a vacuum oven, whereby a powder of the benzoxazine resin as the target compound was obtained. When the molecular weight was measured by GPC, the number average molecular weight (Mn) was 5939 and the weight average molecular weight (Mw) was 17377 in terms of standard polystyrene.
The powder of the benzoxazine resin obtained was heated and pressurized at 100℃or 140℃under 10MPa for 30 minutes using a hot press, to obtain an uncured film. The obtained uncured film was heat-cured at 210℃for 3 hours using a convection oven to obtain a cured film. The properties of the uncured film and the cured film are shown in table 1. In addition, since jeffamine d2000 and hexamethylenediamine are used in a molar ratio of 1:3, the benzoxazine resin obtained in example 5 is also referred to as JD13.
[ Example 6 (JD 19) ]
Bisphenol A (4.5666 g,0.02 mol), hexamethylenediamine (2.0923 g,0.018 mol), jeffamine D2000 (4.0000 g, 0.002mol), paraformaldehyde (2.5840 g,0.086 mol) were added to chloroform (40 mL), and reacted at 60 ℃. After 5 hours, the reaction was stopped. After the reaction solution was cooled to room temperature, 3 times of separation was performed using 60mL of a 0.1N sodium bicarbonate solution. The reaction solution washed with sodium sulfate was dehydrated and filtered. The solvent was removed under heating and reduced pressure with an evaporator, and dried under reduced pressure at 40 ℃ with a vacuum oven, whereby a powder of the benzoxazine resin as the target compound was obtained. When the molecular weight was measured by GPC, the number average molecular weight (Mn) was 6063 and the weight average molecular weight (Mw) was 17414 in terms of standard polystyrene.
The powder of the benzoxazine resin was heated and pressurized at 100℃under 10MPa for 30 minutes using a hot press to obtain an uncured film. The obtained uncured film was heat-cured at 220℃for 2 hours using a convection oven, to obtain a cured film. The properties of the uncured film and the cured film are shown in table 1. In addition, since jeffamine d2000 and hexamethylenediamine are used in a molar ratio of 1:9, the benzoxazine resin obtained in example 6 is also referred to as JD19.
[ Comparative example 1 (C6 Bz 1) ]
To a mixed solvent of toluene (38.6 mL) and isobutanol (6.8 mL), 4.1505g (0.018 mol) of bisphenol A, 2.3243g (0.020 mol) of hexamethylenediamine, 3.6053g (0.120 mol) of paraformaldehyde and 0.5149g (0.005 mol) of phenol were added, and reacted at 90 ℃. After 5 hours, the reaction was stopped. The reaction solution was added to 800mL of methanol to precipitate the target compound. Then, the target compound was isolated by filtration, and dried under reduced pressure at 45℃in a vacuum oven to obtain the target compound. When the molecular weight was measured by GPC, the number average molecular weight (Mn) was 2733, and the weight average molecular weight (Mw) was 7146 in terms of standard polystyrene.
The powder of the benzoxazine resin obtained was heated at 120 ℃ for 40 minutes using a hot press, then heated to 160 ℃ and heated and pressurized under 10MPa for 30 minutes, to obtain an uncured film. Further, it was heat-cured in an oven at 200℃for 1 hour, at 240℃for 1 hour, and at 260℃for 30 minutes to obtain a film-shaped cured product. The properties of the film-like uncured product and cured product are shown in table 1.
[ Comparative example 2 (C6 Bz 2) ]
To chloroform (150 mL) was added 9.5889g (0.042 mol) of bisphenol A, 6.9718g (0.060 mol) of hexamethylenediamine, 7.7485g (0.258 mol) of paraformaldehyde, 3.3887g (0.036 mol) of phenol, and these were reacted at 60 ℃. After 5 hours the reaction was stopped. After the reaction mixture was cooled to room temperature, 3 times of separation was performed with 300mL of a 0.1N sodium hydrogencarbonate solution. The reaction solution washed with sodium sulfate was dehydrated and filtered. The solvent was removed under reduced pressure by heating with an evaporator, and dried under reduced pressure at 40℃with a vacuum oven, whereby the objective compound was obtained. When the molecular weight was measured by GPC, the number average molecular weight (Mn) was 1884 and the weight average molecular weight (Mw) was 3847 in terms of standard polystyrene.
The benzoxazine powder was heated at 120 ℃ for 40 minutes using a hot press, then heated to 160 ℃ and heated and pressurized under 10MPa for 30 minutes to obtain an uncured film. Further, it was heat-cured in an oven at 200℃for 1 hour, at 240℃for 1 hour, and at 260℃for 30 minutes to obtain a film-shaped cured product. The properties of the film-like uncured product and cured product are shown in table 1.
TABLE 1 (TABLE 1-1)
(Tables 1-2)
Determination of the respective powders by uncured powder
In examples 1 to 6 using the diamine compound according to one embodiment of the present invention, film-shaped molded articles were obtained by hot pressing before curing, and it was found that thermoplastic molding was possible before curing. Further, as is clear from table 1, the Tg of each of examples 1 to 6 was lower, the tensile elastic modulus and tensile breaking strength were smaller, and the tensile elongation at break was larger, as compared with comparative examples 1 and 2, in terms of the thermal properties and mechanical properties of the obtained uncured molded articles. Therefore, examples 1 to 6 exhibited more excellent flexibility than comparative examples 1 and 2 in terms of the curing.
In examples 1 to 3, although the alkyl chain was extended, tg was the same level as that of comparative examples 1 and 2, and heat resistance was excellent, as compared with comparative examples 1 and 2, in terms of curing. It was found that the tensile elastic modulus, tensile breaking strength and tensile elongation at break of example 1 were at the same level as those of comparative examples 1 and 2, and the hardness was excellent. On the other hand, examples 2 and 3 were superior in toughness because they were smaller in tensile modulus and tensile breaking strength and larger in tensile elongation at break than comparative examples 1 and 2.
JD11 of example 4 was fully cured at 210 ℃ for 2 hours with a weight reduction of 1.0%. JD13 of example 5 was fully cured at 210 ℃ for 3 hours with a weight reduction of 3.0%. JD19 of example 6 was fully cured at 220 ℃ for 2 hours with a weight reduction of 2.0%. In contrast, the C6Bz2 of comparative example 2 required heating at 240 ℃ for 1 hour and then at 260 ℃ for 30 minutes to achieve complete curing of the resin, with a weight reduction of 9.0%. From the results, it was found that the weight reduction rate, that is, the decomposition rate of the thermosetting resin was reduced by using jeffamine d2000 as the (poly) oxyalkylene diamine compound (C) and hexamethylenediamine as the aliphatic diamine compound (B).
The decomposition start temperature of the uncured film or partially cured film of examples 4 to 6 was 8 to 10℃higher than the decomposition start temperature of the uncured film of comparative example 2. From the results, it was found that the decomposition start temperature was increased by using Jeffamine D2000 as the (poly) oxyalkylene diamine compound (C) and hexamethylenediamine as the aliphatic diamine compound (B).
In addition, the tensile elongation at break of each of examples 4 to 6 was significantly larger than that of comparative examples 1 and 2 in terms of the tensile elongation at break of the uncured film, the partially cured film and the cured film. From the results, it was found that toughness before and after curing was improved by using Jeffamine D2000 as the (poly) oxyalkylene diamine compound (C) and hexamethylenediamine as the aliphatic diamine compound (B).
In comparative examples 1 and 2, the solvents used in the production of the thermosetting resins were different. In comparative example 1, a mixed solvent of a non-halogen hydrocarbon solvent and an aliphatic alcohol solvent was used, while in comparative example 2, a halogen solvent was used alone. As is clear from Table 1, when the mechanical properties of comparative example 1 and comparative example 2 were compared, no large difference was observed between before and after curing. Therefore, it was revealed that the difference in solvent had little influence on the mechanical properties before and after curing.
< Evaluation of reforming Property >
Example 7
On the release PET (thickness: 50 μm), a release PET spacer having a hole (thickness: 50 μm,10cm square) formed in the center was placed, and the resin produced in example 4 was placed in the hole, and the release PET was superimposed thereon. The laminate was sandwiched between stainless steel plates, heated at 160℃for 5 minutes by a press-molding machine, and then press-molded under a pressure of 10MPa for 5 minutes to obtain a film having a thickness of 0.05 mm. The obtained film was fixed to a frame, and along the outer edge of the frame, the end of the film was cut off with a cutter, to obtain a flexible film having self-standing properties. Then, the film was rolled up while being rubbed by hand, and as a result, breakage of the film was not observed. The film was again placed on a frame, and the mold release PET was further sandwiched between stainless steel plates, and after heating at 160℃for 5 minutes by a press molding machine, the film was press molded under a pressure of 10MPa for 5 minutes, resulting in complete recovery of the film having a thickness of 0.05 mm.
From this, it was found that the uncured film or partially cured film obtained from the resin produced in example 4 did not exhibit cracking, crazing, and the like even when subjected to the aggregation or deformation into an arbitrary shape, and thus had excellent toughness. Further, it is understood that the uncured film or the partially cured film of this example has both thermoplastic reforming property and toughness at the time of reforming.
Example 8
On the releasable PET (thickness: 50 μm), a releasable PET spacer having a hole (thickness: 50 μm,10cm square) formed in the center was placed, and the resin produced in example 5 was placed in the hole, and the releasable PET was superimposed thereon. The laminate was sandwiched between stainless steel plates, heated at 140℃for 5 minutes by a press-molding machine, and then press-molded under a pressure of 10MPa for 5 minutes to obtain a film having a thickness of 0.05 mm. The obtained film was fixed to a frame, and along the outer edge of the frame, the end of the film was cut off with a cutter, to obtain a flexible film having self-standing properties. Then, the film was rolled up while being rubbed by hand, and as a result, breakage of the film was not observed. The film was again placed on a frame, and the mold release PET was further sandwiched between stainless steel plates, and after heating at 140℃for 5 minutes by a press-molding machine, the film was press-molded under a pressure of 10MPa for 5 minutes, resulting in complete recovery of the film having a thickness of 0.05 mm.
From this, it was found that the uncured film or partially cured film obtained from the resin produced in example 5 had thermoplastic formability and toughness at the time of forming, and also had thermoplastic formability and toughness at the time of reforming.
[ Example 9 ]
On the releasable PET (thickness: 50 μm), a releasable PET spacer having a hole (thickness: 50 μm,10cm square) in the center was placed, and the resin produced in example 6 was placed in the hole, and the releasable PET was superimposed thereon. The laminate was sandwiched between stainless steel plates, heated at 100℃for 5 minutes by a press-molding machine, and then press-molded under a pressure of 10MPa for 5 minutes to obtain a film having a thickness of 0.05 mm. The obtained film was fixed to a frame, and along the outer edge of the frame, the end of the film was cut off with a cutter, to obtain a flexible film having self-standing properties. Then, the film was rolled up while being rubbed by hand, and as a result, breakage of the film was not observed. The film was again placed on a frame, and the mold release PET was further sandwiched between stainless steel plates, and after heating at 100℃for 5 minutes by a press molding machine, the film was press molded under a pressure of 10MPa for 5 minutes, resulting in complete recovery of the film having a thickness of 0.05 mm.
From this, it was found that the uncured film or partially cured film obtained from the resin produced in example 6 had thermoplastic formability and toughness at the time of forming, and also had thermoplastic formability and toughness at the time of reforming.
[ Comparative example 3]
On the releasable PET (thickness: 50 μm), a releasable PET spacer having a hole (thickness: 50 μm,10cm square) in the center was placed, and the resin produced in comparative example 2 was placed in the hole, and the releasable PET was superimposed thereon. The laminate was sandwiched between stainless steel plates, heated at 100℃for 5 minutes by a press-molding machine, and then press-molded under a pressure of 10MPa for 5 minutes to obtain a film having a thickness of 0.05 mm. The obtained film was fixed to a frame, and along the outer edge of the frame, the end of the film was cut off with a cutter, to obtain a relatively brittle film having self-standing properties. Then, the film was kneaded by hand and agglomerated, with the result that the film was crushed. The crushed film was again placed on a frame, and the film was sandwiched between stainless steel plates, heated at 100℃for 5 minutes by a press-molding machine, and then press-molded under 10MPa for 5 minutes, whereby the film having a thickness of 0.05mm was completely recovered.
[ Comparative example 4]
A film having a thickness of 0.05mm was obtained in the same manner as in comparative example 3, except that the film was press-formed by heating at 160℃for 5 minutes and then under a pressure of 10MPa for 5 minutes by a press-forming machine. The obtained film was fixed to a frame, and along the outer edge of the frame, the end of the film was cut off with a cutter, to obtain a flexible film having self-standing properties. Then, the film was rolled up while being rubbed by hand, and as a result, breakage of the film was not observed. The film was again placed on a frame, and the mold release PET was further sandwiched between stainless steel plates, and after heating at 160℃for 5 minutes by a press-molding machine, press-molding was performed under a pressure of 10MPa for 5 minutes, but as a result, the film having a thickness of 0.05mm was not completely recovered.
TABLE 2
(Table 2)
< Evaluation of softness (mandrel test) >
[ Example 10]
The resin produced in example 6 was heated and pressurized at 100℃and 10MPa for 30 minutes using a hot press (i) to obtain a film (curing degree: 5%). Further, in a convection oven, the films formed from (i) were each subjected to: (ii) Heating at 140℃for 2 hours (degree of cure 22%), (iii) heating at 180℃for 1 hour (degree of cure 55%), (iv) heating at 220℃for 2 hours (degree of cure 100%). Thus, films were obtained (the curing degree was described below for each condition). Thus, 4 films having different degrees of curing were produced. The thickness of each film was 0.125mm.
The degree of cure of each film was calculated from the ratio of the area of the DSC curing exothermic peak of the uncured resin to the area of the DSC curing exothermic peak of the heated film. The film was hung on cylindrical spindles (2 mm to 32 mm) having different diameters using a cylindrical spindle measuring apparatus Elcometer 1500, and both ends of the film were stretched. Softness was evaluated as bending radius (mm) with the corresponding minimum diameter at which no fracture occurred. If the film did not break even with a cylindrical mandrel of minimum diameter (2 mm), the film was bent at an angle of 180 degrees (approximately 0mm in diameter) to evaluate whether the film broken. The results are shown in Table 3.
[ Example 11 ]
The resin produced in example 4 was heated and pressurized at 160℃and 10MPa for 30 minutes by using a hot press to produce a film having a thickness of 0.125 mm. The obtained film was subjected to the same mandrel test as in example 10 to evaluate flexibility. The results are shown in Table 3.
[ Example 12 ]
The resin produced in example 5 was heated and pressurized at 140℃and 10MPa for 30 minutes using a hot press to produce a film having a thickness of 0.125 mm. The obtained film was subjected to the same mandrel test as in example 10 to evaluate flexibility. The results are shown in Table 3.
[ Comparative example 5]
The resin produced in comparative example 2 was heated and pressurized at 100℃under 10MPa for 30 minutes using a hot press to obtain a film having a thickness of 0.125 mm. The obtained film was subjected to the same spindle test as in example 10, but the film was not free-standing, and thus could not be measured.
[ Comparative example 6]
The resin produced in comparative example 2 was heated and pressurized at 160℃and 10MPa for 30 minutes using a hot press, to obtain a film having a thickness of 0.125 mm. The obtained film was subjected to the same mandrel test as in example 10 to evaluate flexibility. The results are shown in Table 3.
TABLE 3
(Table 3)
From these results, it was found that the uncured films or partially cured films obtained from the resins of examples 4 and 5 did not exhibit cracking, and the like even in the softness test (mandrel test) using a cylinder having a diameter of 2mm, and thus had excellent toughness. Further, it was found that even in a 180-degree bending test performed without using a cylinder, no cracking or cracking occurred, and therefore, the alloy had very excellent toughness.
Similarly, it was found that the film having a degree of cure of 5% to 100% obtained from the resin of example 6 had excellent toughness because it did not exhibit cracking, and the like even in the softness test (mandrel test) using a cylinder having a diameter of 2 mm. Further, it was found that the partially cured film having a degree of cure of 5% to 55% was excellent in toughness because it did not exhibit cracking, and the like even in a 180-degree bending test performed without using a cylinder.
< Change in dynamic viscoelasticity (DMA) Curve versus Cure >
[ Example 13 ]
The DMA test described in the column "(4) glass transition temperature (Tg)" was performed on the films produced under the conditions (i) to (iv) described in example 10, the films obtained under the curing conditions heated at 120 ℃ for 0.5 hour (curing degree 11%), and the films obtained under the curing conditions heated at 140 ℃ for 1 hour (curing degree 16%), to measure the change in the DMA curve. The horizontal axis represents temperature (. Degree. C.) and the vertical axis represents storage elastic modulus (Pa). The measurement results are shown in FIG. 1.
As the degree of cure increases, tg was found to shift to the high temperature side and the elastic modulus of the rubbery high elastic region (rubbery plateau zone) increased.
In addition, in the case of a film having a degree of cure of 5% to 55%, it is observed that it has a rubbery high elastic region of the order of 10 6～107 pa·s, and if heated at a temperature corresponding to the region range, the resin is liable to be reformed, so the degree of cure is preferably in the range of 5% to 55%.
< Production of carbon fiber composite Material (CFRP) and evaluation thereof >
(1) Amount of spill (overflow) resin (wt.%)
The weight of the resin overflowed from the CFRP after curing and heating was measured, and the ratio of the overflowed resin to the total amount of the resin impregnated in the carbon fiber before curing was calculated.
(2) Hollow (for 90 degree fiber)
A diamond cutter was used to cut 1cm square from the center portion of the plate-like CFRP, and the square was embedded in an epoxy resin. Next, a cross section including CFRP (a cross section perpendicular to the fiber extending direction) was exposed by slitting with a diamond cutter, and the cross section was polished with a polishing device (MINITECH, manufactured by Presi). Then, the cross section was observed with a digital microscope (VHX-200; manufactured by Keyence Co., ltd.) to evaluate whether or not voids were present in the 90-degree fiber-wrapped surface. Here, "voids present in the 90-degree fiber pack" means: the voids present in the fibers (voids surrounded by the fibers) are seen in a cross section perpendicular to the direction of elongation of the fibers.
(3) Hollow (for resin)
By the same method as in (2) above, the presence or absence of voids in the region consisting of only the resin as seen in the cross section was evaluated.
(4) Discoloration of resin
The presence or absence of discoloration was evaluated for a portion consisting of only a resin as seen in a cross section by the same method as in (2) above.
(5) Storage elastic modulus (E')
The storage elastic modulus E' of CFRP at a measurement frequency of 1Hz and a measurement temperature of 50℃was obtained using a dynamic viscoelasticity measuring apparatus (manufactured by RSA-3, TA Instruments Co.).
(6) Glass transition temperature (Tg)
The glass transition temperature Tg of CFRP was determined using a dynamic viscoelasticity measuring apparatus (RSA-3, manufactured by TA Instruments Co.).
(1. Method for producing film)
[ Example 14 ]
A releasable PET spacer having a hole (thickness: 50 μm,8cm square or 10cm square) in the center was placed on a releasable PET (thickness: 50 μm), and the resin produced in example 6 was placed in the hole, and the releasable PET was superimposed thereon. The laminate was sandwiched between stainless steel plates, heated at 60℃for 5 minutes by a press-molding machine, and then press-molded under a pressure of 10MPa for 10 minutes to obtain a film having a thickness of 0.05 mm.
(2. Method for producing prepreg)
The types of carbon fiber plain weave materials used to make the prepregs are shown below.
PAN carbon fiber (trade name: TR3110M; weight per unit of fiber: 200g/M 2; density: 1.79g/cm 3) manufactured by Mitsubishi chemical Co., ltd
PAN carbon fiber (trade name: CO6343B; fiber unit area weight: 198g/m 2; density: 1.76g/cm 3) manufactured by Toli Co., ltd
The PAN-based carbon fiber manufactured by dori corporation was heated in a convection oven at 300 ℃ for 1.5 hours to remove the sizing agent.
[ Example 15 ]
The film produced in example 14 was laminated on the front and back surfaces of a carbon fiber plain weave material (TR 3110M), sandwiched by stainless steel plates, heated at 60℃for 5 minutes by a press molding machine, and then press molded under a pressure of 1MPa for 10 minutes to obtain a prepreg having a thickness of 0.2 to 0.3 mm. Here, the carbon fiber plain weave material was overlapped with a 8cm square film on the front side and with a 10cm square film on the back side.
[ Example 16]
A prepreg having a thickness of 0.2 to 0.3mm was obtained in the same manner as in example 12, except that the type of the carbon fiber plain weave material was changed to CO 6343B.
(Method for manufacturing CFRP)
[ Example 17 ]
The prepreg manufactured in example 15 was laminated into 10 layers. The obtained laminated prepreg was sandwiched between 2 PI films as release films. Among them, the side surface (thickness portion) of the laminated prepreg is exposed from the PI film. The laminated prepreg sandwiched by PI films was further sandwiched by stainless steel plates, and was cured by a press-forming machine (1) pressing at 60 ℃ for 10 minutes at 1Mpa, (2) then heating to 100 ℃ and pressing at 1Mpa for 20 minutes, (3) then heating to 220 ℃ and pressing at 1Mpa for 2 hours. Thus, a plate-like CFRP having a thickness of about 2mm was obtained. The results are shown in Table 4.
[ Example 18 ]
The prepreg produced in example 16 was laminated into 5 layers. The obtained laminated prepreg was coated with 2 PI films each having a longitudinal direction of 8cm and a transverse direction of 25cm as a release film. The coated laminated prepreg was further sandwiched by stainless steel plates, and was cured by a press-molding machine (1) by pressing at 60℃under 1MPa for 10 minutes, (2) by heating to 100℃and pressing at 1MPa for 20 minutes, (3) by heating to 220℃and pressing at 1MPa for 2 hours. Thus, a plate-like CFRP having a thickness of about 1mm was obtained. The results are shown in Table 4.
[ Example 19 ]
The prepreg produced in example 16 was laminated into 5 layers. The obtained laminated prepreg was coated with 2 PI films each having a longitudinal direction of 8cm and a transverse direction of 25cm as a release film. The coated laminated prepreg was further sandwiched between stainless steel plates, pressed with a press-forming machine (1) at 60℃and 1MPa for 10 minutes, and then heated to 100℃and pressed at 1MPa for 20 minutes, and taken out. The coated laminate prepreg was then cured by heating in a vacuum oven (3) at 220 ℃ for 2 hours. Thus, a plate-like CFRP having a thickness of about 1mm was obtained. The results are shown in Table 4.
[ Example 20 ]
The prepreg produced in example 16 was laminated into 5 layers. The obtained laminated prepreg was coated with 2 PI films each having a longitudinal direction of 8cm and a transverse direction of 25cm as a release film. The coated laminate prepreg was further sandwiched between stainless steel plates, and was taken out in a vacuum press molding machine (1) heated at 100℃for 8 minutes (at atmospheric pressure), (2) then vacuum-pressed at 2MPa for 22 minutes. (3) Then, the temperature was raised to 220℃and vacuum-pressed at 2MPa for 2 hours, thereby curing the same. Thus, a plate-like CFRP having a thickness of about 1mm was obtained. The results are shown in Table 4.
[ Example 21 ]
The prepreg produced in example 16 was laminated into 5 layers. The obtained laminated prepreg was coated with 2 PI films each having a longitudinal direction of 8cm and a transverse direction of 25cm as a release film. The coated laminate prepreg was further sandwiched by stainless steel plates, and cured in a vacuum press-forming machine (1) by heating at 100℃for 7 minutes (at atmospheric pressure), (2) by vacuum-pressing at 2MPa for 23 minutes, (3) by heating to 220℃and vacuum-pressing at 2MPa for 2 hours. Thus, a plate-like CFRP having a thickness of about 1mm was obtained. The results are shown in Table 4.
TABLE 4
As is clear from table 4, thermosetting resins obtained using jeffamine d2000 as the (poly) oxyalkylene diamine compound (C) and hexamethylenediamine as the aliphatic diamine compound (B) can be used favorably for obtaining CFRP.
Further, as is clear from examples 19 to 21, from the viewpoint of preventing discoloration of the resin and preventing occurrence of voids between the resins, it is preferable to remove the sizing agent. In examples 18 to 21, the overflow can be reduced by coating with a PI film. From examples 19 to 21, it is presumed that the use of a vacuum oven or a vacuum press molding machine helps to suppress voids between resins. Although it is presumed that the use of the press-molding machine or the vacuum-press-molding machine can suppress voids between fibers, as shown in examples 17, 18 and 21, the formation of voids between fibers can be further suppressed by increasing the temperature so as not to take out the prepreg from the press-molding machine or the vacuum-press-molding machine.
(Industrial applicability)
The present invention can be used in various fields using thermosetting resins.
Claims (14)
1. A thermosetting resin having a benzoxazine ring structure as shown in the general formula (I) in the main chain,
In the general formula (I),
Ar 1 and Ar 2 each represent a 4-valent aromatic group derived from the difunctional phenol compound (A), ar 1 and Ar 2 are the same or different groups from each other,
N represents an integer of 0 or more,
When n=0, R 1 represents a linear alkylene group having 8 to 12 carbon atoms derived from the aliphatic diamine compound (B), and when n=1 or more, R 1 represents a linear alkylene group having 6 to 12 carbon atoms derived from the aliphatic diamine compound (B),
R 2 represents a (poly) oxyalkylene group derived from a (poly) oxyalkylene diamine compound (C),
In the case where n=0, at least one of the 2 terminals of the main chain is a group represented by the following general formula (II) derived from the monofunctional phenol compound (E), the 2 terminals being the same or different groups from each other,
N=0, m represents an integer of 2 or more, n=1 or more, m represents an integer of 1 or more,
The repeating units represented by m and the repeating units represented by n are repeated in a random manner, or in a block manner, or are alternately copolymerized,
In the general formula (II),
X represents a hydrogen atom or an organic group having 1 to 20 carbon atoms,
L represents an integer of 0 to 3.
2. The thermosetting resin according to claim 1, wherein,
The difunctional phenol compound (A) is selected from the group consisting of 2, 2-bis (4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2-bis (4-hydroxyphenyl) hexafluoropropane, 2-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) diphenylmethane, 2-bis (3-methyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) -2, 2-dichloroethylene, 1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane at least one difunctional phenol compound of 2, 2-bis (4-hydroxy-3-isopropylphenyl) propane, 1, 3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, bis (4-hydroxyphenyl) sulfone, 1, 4-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 5'- (1-methylethylene) -bis [1,1' - (bisphenyl) -2-ol ] propane, 1-bis (4-hydroxyphenyl) -3, 5-trimethylcyclohexane, 1-bis (4-hydroxyphenyl) cyclohexane.
3. The thermosetting resin according to claim 1, wherein,
The (poly) oxyalkylene diamine compound (C) has a (poly) oxyethylene group and/or a (poly) oxypropylene group.
4. The thermosetting resin according to claim 1, wherein,
In the general formula (I), the ratio of m to n is: n/m=1/0.1 to 1/100.
5. A composition of matter comprising a blend of two or more of the above,
A thermosetting resin according to any one of claims 1 to 4.
6. An uncured shaped body is provided, which is formed from a thermoplastic resin,
A method of molding the thermosetting resin according to any one of claims 1 to 4.
7. The uncured shaped body according to claim 6, wherein,
The bending radius of the uncured molded article was 2mm or less under a mandrel test conducted in accordance with JIS K-5600-5-1:1999.
8. A partially cured shaped body which has been cured,
A thermosetting resin according to any one of claims 1 to 4, wherein the thermosetting resin is partially cured to a degree of curing of 1 to 99%.
9. The partially cured molded body of claim 8, wherein,
The partially cured molded body has a bending radius of 2mm or less under a mandrel test according to JIS K-5600-5-1:1999.
10. A cured molded article comprising a cured resin and a cured resin,
A cured product of the thermosetting resin according to any one of claims 1 to 4.
11. The cured molded body according to claim 10, wherein,
The bending radius of the cured molded article was 2mm or less under a mandrel test according to JIS K-5600-5-1:1999.
12. A thermosetting resin having a benzoxazine ring structure in its main chain, wherein,
An uncured molded article obtained by molding the thermosetting resin and having a degree of cure of less than 1%, or a partially cured molded article obtained by curing the thermosetting resin and having a degree of cure of 1 to 99%, has thermoplastic reshaping properties and toughness,
The thermoplastic reshaping properties refer to the following properties: the uncured molded body or the partially cured molded body is deformed into an arbitrary shape and then returns to a shape before deformation when heated at 200 ℃ or less,
The toughness refers to the following properties: compared with the heating before and after, the uncured shaped body or the partially cured shaped body does not generate cracks or fissures,
The thermosetting resin has a repeating thermoplastic, which means: the reshaping property and the toughness can be maintained even if subjected to the deformation and the heating more than 1 time.
13. A process for producing a thermosetting resin,
Wherein the main chain of the thermosetting resin has a benzoxazine ring structure,
The method for producing the thermosetting resin comprises the following steps:
step (s 1) of reacting a difunctional phenol compound (a), an aliphatic diamine compound (B) and an aldehyde compound (D);
an optional step (s 2) of reacting the difunctional phenol compound (A), (poly) oxyalkylene diamine compound (C) and aldehyde compound (D); and
An optional step (s 3) of reacting the monofunctional phenol compound (E),
And
In the case where step (s 2) is not included, the method for producing a thermosetting resin includes step (s 3),
In the case where step (s 2) is included, the aliphatic diamine compound (B) is an aliphatic diamine having a linear alkylene group having 6 to 12 carbon atoms, in the case where step (s 2) is not included, the aliphatic diamine compound (B) is an aliphatic diamine having a linear alkylene group having 8 to 12 carbon atoms,
The (poly) oxyalkylene diamine compound (C) has a (poly) oxyethylene group and/or a (poly) oxypropylene group.
14. The method for producing a thermosetting resin according to claim 13, wherein,
The molar ratio of the aliphatic diamine compound (B) to the (poly) oxyalkylene diamine compound (C) is: (poly) oxyalkylene diamine compound (C)/aliphatic diamine compound (B) =1/0.1 to 1/100.
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| JP2022019839 | 2022-02-10 | ||
| JP2022-019839 | 2022-02-10 | ||
| PCT/JP2022/037971 WO2023063334A1 (en) | 2021-10-12 | 2022-10-12 | Heat-curable resin, composition, uncured molded object, partly cured molded object, cured molded object, and method for producing heat-curable resin |
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