CN112771103A - 纤维强化复合材料用树脂组合物及使用其的纤维强化复合材料 - Google Patents
纤维强化复合材料用树脂组合物及使用其的纤维强化复合材料 Download PDFInfo
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- CN112771103A CN112771103A CN201980062620.9A CN201980062620A CN112771103A CN 112771103 A CN112771103 A CN 112771103A CN 201980062620 A CN201980062620 A CN 201980062620A CN 112771103 A CN112771103 A CN 112771103A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
- C08G59/46—Amides together with other curing agents
- C08G59/48—Amides together with other curing agents with polycarboxylic acids, or with anhydrides, halides or low-molecular-weight esters thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
- B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
- C08G59/46—Amides together with other curing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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Abstract
提供一种树脂组合物,其对强化纤维的含浸性、快速硬化性优异,硬化时而得的成形物的耐热性高,短时间内的生产性优异且适合作为纤维强化复合材料的基质树脂。一种纤维强化复合材料用树脂组合物,包括:主剂,包含环氧树脂(A)以及下述通式(1)所表示的酯化合物(B);以及硬化剂,包含胺化合物(C),且所述纤维强化复合材料用树脂组合物为二液硬化型。(R1及R2表示烷基或芳基,R1与R2可相互连结而形成环状结构。另外,R1可为含酯基。)
Description
技术领域
本发明涉及一种粘度低且短时间内的硬化性优异的纤维强化复合材料用的树脂组合物、使用其的纤维强化复合材料及使用其的纤维强化成形体的制造方法。
背景技术
一般而言,纤维强化复合材料包含玻璃纤维、聚芳酰胺(aramide)纤维或碳纤维等强化纤维及不饱和聚酯树脂、乙烯酯树脂、环氧树脂、酚树脂、苯并噁嗪树脂、氰酸酯树脂、双马来酰亚胺树脂等热硬化性基质树脂,就轻量且强度、耐腐蚀性或耐疲劳性等机械物性优异的方面而言,作为飞机、汽车、土木建筑及运动用品等的结构材料而广泛适用。
纤维强化复合材料的制造方法是通过以下方法而实施:使用将热硬化性的基质树脂预先含浸于强化纤维所得的预浸体的高压釜成形法或压制成形法;或包括使液状的基质树脂含浸于强化纤维的步骤及通过热硬化而进行的成形步骤的树脂转注成形法(resintransfer molding method)、液体压缩成形法(liquid compression molding method)、湿敷(wet lay-up)成形法、拉拔成形法或长丝缠绕(filament winding)成形法等。其中,不使用预浸体来进行含浸与成形的树脂转注等成形法中,为使强化纤维快速地含浸,而使用低粘度的基质树脂。
此外,在树脂转注成形法、液体压缩成形法中,为了确保高生产性,要求在使树脂含浸于强化纤维后,硬化速度快的基质树脂。进而,在这些成形法中,包括在硬化后将成形物自模具脱模的步骤,为了确保高生产性,要求不仅硬化速度快而且脱模性也优异的基质树脂组合物。
以往,在树脂转注成形法、液体压缩成形法中,一直使用不饱和聚酯树脂、乙烯酯树脂、氨基甲酸酯树脂或环氧树脂等热硬化性树脂。具有自由基聚合性的不饱和聚酯树脂、乙烯酯树脂虽然粘度低且快速硬化性优异,但有成形时的硬化收缩大,成形物的耐热性、强度或韧性等机械物性相对低的课题。氨基甲酸酯树脂的快速硬化性优异,可获得强度或韧性高的成形物,但有成形物的耐热性低、吸水率高的课题。环氧树脂虽然可获得耐热性、强度或韧性高的成形物,但有快速硬化性差的课题。
专利文献1中,虽然尝试通过环氧树脂与特定的酚化合物的组合来对树脂组合物赋予快速硬化性,但至凝胶化为止的时间长,快速硬化性不足,耐热性也差。
专利文献2、专利文献3中,尝试通过在包含环氧树脂与聚乙烯多胺的树脂组合物中添加特定的催化剂来赋予快速硬化性。但是,至凝胶化为止的时间长,快速硬化性不足。
专利文献4中,尝试通过环氧树脂与特定的胺化合物、酚化合物的组合来对树脂组合物赋予快速硬化性,但仍然是快速硬化性不足。
专利文献5、专利文献6、专利文献7、专利文献8中,提出了使用内酯化合物的环氧树脂组合物,但并非表现二液硬化型的快速硬化性的环氧树脂组合物。
关于纤维强化复合材料的基质树脂,为使低粘度性优异且不降低耐热性、进而确保高生产性,期望快速硬化性的进一步提升。
现有技术文献
专利文献
专利文献1:日本专利特开2016-098322号公报
专利文献2:日本专利特表2015-535022号公报
专利文献3:日本专利特表2015-536373号公报
专利文献4:WO2017/179358号公报
专利文献5:日本专利特开2013-32510号公报
专利文献6:日本专利特表2008-530321号公报
专利文献7:日本专利特开平11-158350号公报
专利文献8:日本专利特开平3-2258号公报
发明内容
本发明的目的在于提供一种无损低粘度性与耐热性、且快速硬化性优异的纤维强化复合材料用的树脂组合物。进而,目的在于提供一种可生产性良好地获得纤维强化复合材料(纤维强化成形体)的树脂组合物或使用其的预浸体、纤维强化成形体的制造方法。
本发明人等人为解决所述课题而进行研究,结果发现,通过使用包含特定的环氧树脂以及酯化合物的主剂、以及包含特定的胺化合物的硬化剂,而解决所述课题,从而完成本发明。
即,本发明为一种纤维强化复合材料用树脂组合物,包括:主剂,包含环氧树脂(A)以及下述通式(1)所表示的酯化合物(B);以及硬化剂,包含胺化合物(C),且所述纤维强化复合材料用树脂组合物为二液硬化型。
[化1]
(式中,R1及R2表示碳原子数1~40的烷基或碳原子数6~40的芳基,R1与R2可相互连结而形成环状结构。另外,R1可为R23OCO-所表示的基,R23与R1、R2同义。)
作为所述酯化合物(B),可列举由下述通式(2)~通式(4)中的任一者所表示的酯化合物。
[化2]
(式中的R3~R22为氢原子、羟基、碳原子数1~20的直链或分支的烷基、碳原子数6~20的芳基、碳原子数3~20的杂芳基或由R23OCO-所表示的基,在芳基、杂芳基或R23OCO-基的情况下,它们可直接键结于芳香族骨架或六元内酯骨架(在R17的情况下,为其所键结的碳原子),也可经由交联基键结。)
作为所述胺化合物(C),可列举由下述通式(5)所表示的胺化合物。优选为由下述式(6)~式(8)所表示的胺化合物。
X-(CH2NH2)n (5)
(式中,X表示碳数1~16的n价有机基,n表示2或3。)
[化3]
满足主剂与硬化剂的质量比为90:10~70:30的范围、主剂中含有2重量%~30重量%的酯化合物(B)、或纤维强化复合材料用树脂组合物的硬化物的玻璃化温度显示100℃以上中的任一个以上为优选形态。
另外,本发明为一种预浸体,其特征在于,在所述纤维强化复合材料用树脂组合物中调配强化纤维而成。所述预浸体中,强化纤维的体积含有率可为45%~70%。
进而,本发明为所述预浸体的硬化物。
另外,本发明为一种成形体的制造方法,其特征在于,利用树脂转注成形法、或液体压缩成形法将所述预浸体成形。
另外,本发明为一种成形体的制造方法,其特征在于包括如下步骤,所述步骤包括:准备所述二液硬化型的纤维强化复合材料用树脂组合物;将所述纤维强化复合材料用树脂组合物的二液与强化纤维混合而制成预浸体;继而利用模具将所述预浸体加热硬化而成形。
本发明的纤维强化复合材料用树脂组合物的粘度低,具有良好的对强化纤维的含浸性,且显示出短时间内的硬化性。因此,适合作为用以通过树脂转注成形法或液体压缩成形法将预浸体制成成形体的纤维强化复合材料用树脂组合物。进而,硬化而得的成形物为自模具的脱模性优异,且玻璃化温度高的成形物。
具体实施方式
以下,对本发明的实施方式进行详细说明。
本发明的纤维强化复合材料用树脂组合物在其中调配强化纤维而形成预浸体,且通过将所述预浸体硬化或成形而形成硬化物或成形体。以下,也将纤维强化复合材料用树脂组合物称为树脂组合物,也将纤维强化复合材料称为复合材料、成形体或硬化物。
本发明的树脂组合物为包括主剂及硬化剂的二液硬化型的树脂组合物,所述主剂包含环氧树脂(A)以及所述式(1)所表示的酯化合物(B),所述硬化剂包含胺化合物(C)。此处,也将所述环氧树脂(A)、酯化合物(B)、胺化合物(C)分别称为(A)成分、(B)成分、及(C)成分,或者环氧树脂、酯化合物、胺化合物。
用作主剂成分的环氧树脂(A)可优选地使用二官能以上的环氧树脂。具体而言,可使用双酚A型环氧树脂、双酚F型环氧树脂、双酚E型环氧树脂、双酚S型环氧树脂、双酚Z型环氧树脂、异佛尔酮双酚型环氧树脂等双酚型环氧树脂;这些双酚型环氧树脂的卤素、烷基取代物、氢化物等、以及不限于单量体而具有多个重复单元的高分子量体;环氧烷加成物的缩水甘油醚;苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、双酚A酚醛清漆型环氧树脂等酚醛清漆型环氧树脂;3,4-环氧基-6-甲基环己基甲基-3,4-环氧基-6-甲基环己烷羧酸酯、3,4-环氧基环己基甲基-3,4-环氧基环己烷羧酸酯、1-环氧基乙基-3,4-环氧基环己烷等脂环式环氧树脂;三羟甲基丙烷聚缩水甘油醚、季戊四醇聚缩水甘油醚、聚氧亚烷基二缩水甘油醚等脂肪族环氧树脂;邻苯二甲酸二缩水甘油酯、四氢邻苯二甲酸二缩水甘油酯、二聚酸缩水甘油酯等缩水甘油酯;四缩水甘油基二氨基二苯基甲烷、四缩水甘油基二氨基二苯基砜、三缩水甘油基氨基苯酚、三缩水甘油基氨基甲酚、四缩水甘油基亚二甲苯二胺等缩水甘油胺类等。这些可单独使用一种,也可组合使用两种以上。
就流动性的观点而言,环氧树脂的25℃下的粘度优选为30000mPa·s以下。再者,本说明书中,只要无特别说明,则粘度是通过E型粘度计进行测定。
用作主剂成分的酯化合物(B)为所述通式(1)所表示的酯化合物。它们通过具有酯结构,而与胺化合物反应,由此生成羟基,提高快速硬化性。
通式(1)中,R1及R2表示碳原子数1~40的烷基或碳原子数6~40的芳基,但优选为碳原子数1~10的烷基或6~20的芳基。就生成酚性羟基的观点而言,R2优选为芳基。另外,R1与R2可相互连结而形成环状结构,所述烷基或芳基可具有取代基。优选的取代基为羟基、羧基、硫醇基、酯基(OCO)等。另外,R1可为含酯基(R23OCO-)。此处,R23与R1、R2同义,与酯基的氧或碳键结。另外,R1及R2可具有取代基。所述取代基能够根据通式(2)~通式(4)的说明理解。
这些中,特别是所述通式(2)~通式(4)所表示的酯化合物通过与胺化合物反应而生成酚性羟基,进而提高快速硬化性,故优选。
通式(2)~通式(4)中,R3~R22为氢原子、羟基、碳原子数1~20的直链或分支的烷基、碳原子数6~20的芳基、碳原子数3~20的杂芳基或由R23OCO-所表示的基,在芳基、杂芳基或R23OCO-基的情况下,它们可直接键结于芳香族骨架或六元内酯骨架,也可经由交联基键结。此处,R17未与环构成碳原子键结,因此可与其所键结的碳原子直接或经由交联基键结。R23与所述烷基或芳基同义。优选的交联基为碳数1~3的亚烷基等。
在为所述烷基、芳基或杂芳基(包括R23为烷基或芳基的情况)时,它们可具有取代基,优选的取代基为羟基、羧基、硫醇基、酯基(OCO)等。
以下示出通式(1)或通式(2)~通式(4)所表示的化合物的具体结构式的例子。这些可单独使用一种,也可视需要使用两种以上。
[化4]
用作硬化剂成分的胺化合物(C)为具有氨基的化合物,但优选为所述通式(5)所表示的化合物。通式(5)所表示的胺化合物(C)在一分子中具有两个或三个氨基甲基。氨基甲基与环氧基或丙烯酰基的反应性高,快速硬化性优异。另外,通过在一分子中具有两个以上的氨基甲基,可获得加热硬化时交联密度高且耐热性优异的成形物。
作为胺化合物(C)的具体例,可列举:分子结构中具有式(9)所表示的二级胺的亚氨基双丙胺、三亚乙基四胺、双(六亚甲基)三胺等非环式脂肪族多胺、双(氨基甲基)环己烷、1,3,6-三氨基甲基环己烷、3,9-双(3-氨基丙基)-2,4,8,10-四氧杂螺(5.5)十一烷、双(氨基甲基)降冰片烷等环状脂肪族多胺、间苯二甲胺(m-Xylylenediamine,MXDA)等包含芳香环的多胺、及在它们的脂环或芳香环上取代有烷基的衍生物。
[化5]
这些中,特别优选为所述式(6)所表示的降冰片烷二胺、所述式(7)所表示的1,3-双(氨基甲基)环己烷、或所述式(8)所表示的三亚乙基四胺。通过制成这些胺化合物,快速硬化性提高。这些分别可单独使用,也可混合使用。
本发明的树脂组合物为主剂与硬化剂的二液硬化型,通过将这些以规定的比例混合,而能够加热硬化。所述主剂与硬化剂的混合比率是根据主剂中的环氧树脂成分与硬化剂中的硬化剂成分的种类而决定。具体而言,计算所有环氧树脂成分中所含的环氧基的摩尔数及硬化剂成分中所含的活性氢的摩尔数的比率而加以调整,质量比为90:10~70:30的范围。若为所述范围,则所获得的树脂硬化物的耐热性或弹性系数优异。
主剂中理想的是以2质量%~30质量%的范围包含酯化合物(B)。若含有率过低,则快速硬化性无法充分显现。另一方面,若含有率过高,则耐热性下降。
本发明的树脂组合物为主剂与硬化剂的二液硬化型,包含所述胺化合物的硬化剂视需要可包含其他硬化剂成分、硬化促进剂或硬化催化剂。
另外,在主剂及硬化剂中,也可适当调配塑化剂、染料、有机颜料或无机填充剂、高分子化合物、偶合剂、表面活性剂及溶剂等作为其他成分。另外,也可调配其他硬化性树脂。作为此种硬化性树脂,可列举不饱和聚酯树脂、硬化性丙烯酸树脂、硬化性氨基树脂、硬化性三聚氰胺树脂、硬化性脲树脂、硬化性氰酸酯树脂、硬化性氨基甲酸酯树脂、硬化性氧杂环丁烷树脂、硬化性环氧基/氧杂环丁烷复合树脂等,但并不限定于这些。
可考虑与主剂及硬化剂中所含的成分的反应性或粘度等,任意调配这些成分。避免与主剂或硬化剂中所含的成分进行反应的调配。另外,溶剂会使成形体的生产性下降,故理想的是不含或为少量。
作为所述其他硬化剂成分或硬化促进剂、硬化催化剂,例如可列举:三级胺、羧酸、磺酸、路易斯酸络合物、鎓盐、咪唑、醇类、或苯酚、甲酚、烯丙基苯酚(allyl phenol)、硝基苯酚、对氨基苯酚、间氨基苯酚、单-叔丁基苯酚、二-叔丁基苯酚等具有一个酚性羟基的化合物等。这些可使用一种或两种以上。
本发明的树脂组合物的成为硬化物时的玻璃化温度(Tg)优选为100℃以上。在Tg低于100℃的情况下,当将所获得的纤维强化复合材料的硬化物或成形体自模具脱模时容易变形。
作为本发明的纤维强化复合材料中使用的强化纤维,选自玻璃纤维、聚芳酰胺纤维、碳纤维、硼纤维等中,但为了获得强度优异的纤维强化复合材料,优选为使用碳纤维。
本发明的预浸体包含所述树脂组合物及强化纤维。预浸体中的强化纤维的体积含有率优选为45%~70%,更优选为48%~62%的范围。通过设为所述范围,可获得空隙少且强化纤维的体积含有率高的成形体,因而可获得强度优异的成形材料。
预浸体的硬化可优选地通过以下方式来进行:将主剂以50℃~90℃的范围、将硬化剂以20℃~60℃的范围的温度注入至预先配置有纤维的模具等中,以90℃~160℃的温度、优选为100℃~140℃加热硬化15秒~360秒的时间、优选为25秒~150秒。主剂与硬化剂可同时注入至模具中,为了提高均匀性,理想的是之前混合后进行注入。但是,也可不进行混合而注入至模具中,并在纤维的存在下进行混合。作为混合方式,冲突混合、静态混合器方式等并无特别限制,优选为短时间内完成均匀混合的冲突混合方式。
若注入温度低,则流动性下降,从而导致对成形模具及纤维的填充不良而欠佳。另外,若注入温度高,则产生飞边,或在注入时开始树脂的硬化,在槽内或成形模具内的树脂发生硬化,产生填充不良,因而欠佳。另外,若成形时间过短,则无法充分填充,若过长,则模具内的树脂硬化而导致成形不良,并且导致生产性的下降,因而欠佳。本发明的预浸体中所含的树脂组合物能够在如所述那样的较低注入温度下注入、含浸于成形模具,另外可获得以短的硬化时间完成自模具的脱模的硬化物。
由本发明的树脂组合物来制作预浸体或纤维强化复合材料(成形体或硬化物)的方法并无特别限定,适宜为树脂转注成形(resin transfer molding,RTM)法或液体压缩成形(liquid compression molding,LCM)法。所谓RTM法,是指将包含强化纤维的纤维基材或预成形体设置于成形模具内,在所述成形模具内注入液状的纤维强化复合材料用树脂组合物而使其含浸于强化纤维,制成预浸体,其后进行加热而使预浸体硬化,从而获得成形体的方法。硬化条件适宜为所述预浸体的硬化中所说明的条件。所谓LCM法,是指将包含预先融合有树脂的强化纤维的纤维基材或预成形体,在释放了成形压力的状态下设置于成形模具内,并将成形模具合模,由此而同时进行含浸与成形,并在制成预备成形体后将模具加热而使预备成形体硬化,从而获得成形体的方法。LCM法的硬化条件也适宜为所述预浸体的硬化中所说明的条件。
实施例
接下来,基于实施例对本发明进行具体的说明,但本发明只要不超过其主旨,则并不限定于以下的实施例。表示调配量的份只要无特别说明则为质量份。
实施例及比较例中使用的各成分的简称如下所述。
(A)成分
YD-128:双酚A型环氧树脂(新日铁住金化学公司制造)
YDF-170:双酚F型环氧树脂(新日铁住金化学公司制造)
(B)成分
DHCM:二氢香豆素
SAPE:水杨酸苯酯
(C)成分
NBDA:双(氨基甲基)降冰片烷
1,3-BAC:1,3-双氨基甲基环己烷
TETA:三亚乙基四胺
(D)成分(其他成分)
4tBP:4-叔丁基苯酚
2E4MZ:2-乙基-4-甲基咪唑
DICY:二氰二胺
各物性的测定或试验方法如下所述。
(主剂粘度的测定)
使用锥板型E型粘度计(东机产业股份有限公司:RE80H),在25℃下测定。将自测定开始经过60秒后的值设为粘度的值。
(凝胶时间的测定)
在预先加热至120℃的凝胶化试验机(日新科学制造)的板上添加二液硬化型树脂组合物,使用氟树脂棒以一秒钟转两下的速度搅拌,进行树脂组合物的硬化,直至失去塑化性所需的时间设为凝胶化时间。不进行凝胶化时设为×。
(玻璃化温度Tg的测定)
使用动态粘弹性试验机,在升温速度5℃/分钟、弯曲模式、测定频率10Hz的条件下测定玻璃化温度测定用试验片,将损失弹性系数(E")的最大值作为Tg。
实施例1
使用95份的作为(A)成分的YD-128,使用5份的作为(B)成分的DHCM,使用20.9份的作为(C)成分的NBDA。
将(A)成分与(B)成分混合来制成主剂。将(C)成分与(D)成分混合来制成硬化剂。
使用真空混合器,将主剂与硬化剂在室温下一面搅拌一面混合,获得树脂组合物。
将所述树脂组合物流入挖通为平板形状且设置有4mm厚的间隔件的纵60mm×横80mm的加热至120℃的模具中,进行5分钟硬化后,使用台式带锯将所获得的硬化物切削为50mm×10mm的大小而获得试验片,将其用于Tg的测定。
实施例2~实施例7、比较例1~比较例8
以表1及表2所记载的组成(份)使用各原料来作为(A)成分~(D)成分,除此以外,以与实施例1相同的混合条件制作树脂组合物及试验片。
将实施例1~实施例7的调配、试验结果示于表1中,将比较例1~比较例8的调配、试验结果示于表2中。调配量的数字为质量份。
[表1]
[表2]
Claims (12)
3.根据权利要求1所述的纤维强化复合材料用树脂组合物,其特征在于,胺化合物(C)由下述通式(5)所表示。
X-(CH2NH2)n (5)
(式中,X表示碳数1~16的n价有机基,n表示2或3。)
5.根据权利要求1所述的纤维强化复合材料用树脂组合物,其特征在于,主剂与硬化剂的质量比为90:10~70:30的范围。
6.根据权利要求1所述的纤维强化复合材料用树脂组合物,其特征在于,主剂中含有2重量%~30重量%的酯化合物(B)。
7.根据权利要求1所述的纤维强化复合材料用树脂组合物,其特征在于,纤维强化复合材料用树脂组合物的硬化物的玻璃化温度显示100℃以上。
8.一种预浸体,其特征在于,在如权利要求1至7中任一项所述的纤维强化复合材料用树脂组合物中调配强化纤维而成。
9.根据权利要求8所述的预浸体,其中,强化纤维的体积含有率为45%~70%。
10.一种硬化物,为如权利要求8所述的预浸体的硬化物。
11.一种成形体的制造方法,其特征在于,利用树脂转注成形法、或液体压缩成形法将如权利要求8所述的预浸体成形。
12.一种成形体的制造方法,其特征在于包括如下步骤:准备如权利要求1所述的二液硬化型的纤维强化复合材料用树脂组合物;将所述纤维强化复合材料用树脂组合物的二液与强化纤维混合而制成预浸体;继而利用模具将所述预浸体加热硬化而成形。
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