JP2663113B2 - Manufacturing method of composite material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to mechanical strength and heat resistance.
Composite material with excellent propertiesChargeFurther details on the manufacturing method
Constitutes a clay mineral with a resin composition containing polyamide
The silicate layer bonds to each other via ionic bonds,
Is evenly mixed, and the machine
With excellent mechanical strengthChargeRelated to the manufacturing method
You. [0002] 2. Description of the Related Art Conventionally, mechanical properties of organic polymer materials
To improve calcium carbonate, clay minerals, mica, etc.
Addition and mixing of inorganic materials are being studied. [0003] However, these inorganic materials are added and mixed.
When combined, the organic polymer matrix in the organic polymer material
The bond between them is very weak.
There is a problem and the amount of inorganic material added is limited.
You. An eye that strengthens the bond between this inorganic material and the polymer material
Treatment of the inorganic material with a silane coupling agent
Etc. are known. However, obtained by these methods
The bond between organic polymer materials and inorganic materials is
It is due to the Wales coupling, and the familiarity between the two
It is a degree to improve, and for the reinforcement effect and heat resistance improvement
It cannot be enough. [0004] To solve these problems, the present applicant has
First, the resin containing polyamide and the polyamide
From the vermiculite flakes with an average dispersed aspect ratio of 5 or more
"Resin composition containing polyamide" (JP-A-57-878)
3551). This composition is contained in the resin
Vermiculite thin with large aspect ratio (particle size / thickness)
By mixing pieces, the mechanical strength of the organic polymer material
The goal is to improve the degree. [0005] However, this tree
The fat composition has certainly higher mechanical strength than the conventional one.
Improved, but requires mechanical grinding to obtain vermiculite flakes
Therefore, a sufficient aspect ratio cannot be obtained. Only
However, since the bonding strength between the mineral layer and the matrix is weak, the required strength
To achieve this, it is necessary to increase the amount of addition at the expense of embrittlement.
Was. [0006] In addition, polyamide and poly
Attempting to obtain a composite material by synthesizing polymers such as styrene
("Polymer", 19, 759, 1)
979; "Industrial materials", 25, "3", 58, 197
7). However, in the conventional methods, organic polymer chains are not sufficient.
This distance does not penetrate between clay mineral layers.
The silicate layer and the organic polymer
First, the silicate constituent unit layer is molecularly dispersed.
I never did. In such a case,
Increases mechanical strength by reducing mineral aspect ratio
Has the opposite effect. In addition, the polymer phase and the matrix
Sufficient reinforcement effect due to insufficient bond with intermetallic compound
Was not obtained. It also contains at least one amino group.
Organic compounds that have lactam polymerization catalytic action
Existence of clay-organic complex bonded to clay by heat exchange reaction
"Clay-polyamide composite" that polymerizes lactam in the presence
Production Method of Body "(Japanese Patent Laid-Open No. 51-109998)
Proposed. However, this clay-polyamide composite
The composite obtained by the production method of
These are not separated for each crystal unit layer.
The interlaminar distance is small, so the tensile strength is
Below the strength of the resin. That is, for example, Niro
The tensile strength is not more than the tensile strength of
The tensile strength disclosed in the example is 30-80% of nylon 6.
Is). Therefore, the complex obtained by this method is
Problems with insufficient mechanical strength and heat resistance
doing. In the first place, clay has conventionally been used in polyamides.
Is dispersed and hybridized.
It is also said that mechanical strength such as tensile strength decreases.
You. Japanese Patent Application Laid-Open No. 51-109998 discloses the method.
The composite obtained by the method has the strength of this conventional composite.
Molded product obtained by using matrix resin alone with improved reduction
The strength of the object, in other words, what
Molded product obtained from the original resin alone by compounding
The mechanical strength is further reduced. Thus, on
In the method described above, the molded article obtained from the matrix resin alone
It is possible to obtain a composite having strength characteristics superior to strength.
Have the problem of not being able to. Therefore, the present inventors have proposed the conventional
Intensive research is carried out to solve technical problems, and various systematic
As a result of repeated experiments, the present invention has been accomplished. (Object of the Invention) An object of the present invention is to provide a composite having excellent mechanical strength and heat resistance.
LumberChargeIt is to provide a manufacturing method. Other objects of the present invention
Has better mechanical strength than resin as matrix
And heat-resistant composite materialsChargeTo provide a manufacturing method
You. The present inventors have addressed the above-mentioned problems of the prior art.
In this regard, I focused on the following. That is, first,
More proposed clay-polyamide composites are
When clay is dispersed in mid and hybridized,
The mechanical strength such as tensile strength is lower than that of the resin.
This is a conventionally proposed clay-polyamide composite.
The body has a weak bond between the clay layer and the polyamide, dispersing the clay layer
The tensile strength is not enough
Less than the resin strength (eg less than the tensile strength of nylon 6)
(Below). Also, the dispersed clay layer
It turned out that the constituent units of itself were large. The present inventors have developed a method for solving these problems.
Silicate layer to be dispersed in resin
The silicate layer and the polyamide molecular chain by ionic bonding.
And disperse the silicate layer evenly in the resin.
The distance between the silicate layers dispersed in the resin is 1
The focus was on making the temperature over 00 °. As a method for realizing this, a positive
On-exchange capacity is appropriate (for example, 50 to 200 meq /
100g) clay mineral, polyamide mono
Polyamide monomer molecules besides
Coexist with a substance that exhibits a very strong catalytic action
To increase the distance between clay layers appropriately before polymerization
The silicate layer and the polyamide molecular chains
Coexisting substances that are bonded by on-bond,
I paid attention. And a material that satisfies the above and
And (a) copper ion, hydrogen ion, aluminum ion
Or a swelling agent comprising an inorganic cation such as (b) carbon
Having an alkylene group of 12 or more and a carboxyl group
Of organic cations (organic ammonium ions)
We focused on the wetting agent. Then, the predetermined cation exchange is performed in advance.
Contacting the clay mineral having the exchange capacity with the swelling agent
The two are ion-bonded to each other,
Creates a complex that swells with monomer at temperature
And mixing the composite with a polyamide monomer.
The compound is heated to a predetermined temperature to act as a catalyst for the swelling agent.
Excellent mechanical strength and heat resistance
Thus, the present invention has been achieved. [0014] [Means for Solving the Problems](First Invention: Method for Manufacturing Composite Material) The method for producing a composite material of the present invention has a cation exchange capacity of 5
0-200 meq / 100 g clay mineral and copper ion
, Hydrogen ion, aluminum ionMore than one kind ofInorganic
A swelling agent consisting of a cation is brought into contact with
Attach the monomer at a temperature above the melting temperature of the monomer.
Contacting process to form a composite having the property of swelling due to
And a step of mixing the composite with a polyamide monomer
And the mixtureAddHeating and under the catalytic action of the swelling agent
And a polymerization step of polymerizing the polymer.
And a resin that is uniformly and molecularly dispersed in the resin.
A silicate layer comprising:
Has a thickness of 7 to 12 mm and a distance between silicate layers of 100 mm or less
And the silicate layer has a negative charge、 PoLiam
Forms an ionic bond with the positively charged group of some of the
And the area per one valence of the negative charge is 25 to 200 mm.²
And the silicate layer is a polymer chain of the polyamide.
Ionic bond with a part of
0.5 to 150 parts by weight per 100 parts by weight,
Obtaining a composite material with excellent mechanical strength and heat resistance
Characterized by the following.[0016] The composite material of the present inventionChargeManufacturing method has excellent effects
The mechanism to be exerted is not always clear.
There is not, but it is thought as follows.[0017] First, the method for producing a composite material of the present invention
An ion exchange capacity of 50 to 200 meq / 100 g
Earth minerals, copper ion, hydrogen ion, aluminum ion
Contact with a swelling agent consisting of inorganic cations such as
Both are ion-bonded to form a complex (contact step). This
As a result, the swelling agent is adsorbed on the clay mineral,
Swells with monomers at temperatures above the melting temperature of
A complex having Where the clay mineral is
Cation exchange capacity 50-200 meq / 100g
And a clay mineral with a large contact area with the monomer to be reacted
It is. By setting the exchange capacity to the above range, inorganic
The swelling agent consisting of cations can be sufficiently exchanged and adsorbed.
Before the polymerization, the distance between the layers of the kamo clay mineral itself is moderately enlarged.
Can be Next, obtained in the contacting step
Mix the composite and polyamide monomer (mixing process
About). Next, the mixture obtained in the mixing step is
By heating to a predetermined temperature, the weight
(Polymerization step). As a result, a tree containing polyamide
Fat and silicate uniformly and molecularly dispersed in the resin
A silicate layer having a thickness of 7
~ 12mm, the distance between silicate layers is more than 100mm,
Moreover, the silicate layer has a negative charge and the polyamide in the resin
Forms an ionic bond with the positively charged group of some of
And the area per one valence of the negative charge is 25 to 200Å.²so
And the silicate layer is formed of a polymer chain of the polyamide.
It is ionically bonded to a part and the content of the silicate layer is
A machine which is 0.5 to 150 parts by weight with respect to 00 parts by weight
Composite material with excellent mechanical strength and heat resistance
You. At this time,Copper ion, aluminum ion, hydrogen ion
onSwelling agents composed of inorganic cations such as
Lactam compound
Has the action of initiating ring-opening polymerization, and is produced as the polymerization reaction progresses.
It also has the effect of taking in polymers between layers. this is,
The swelling agent has a strong force to capture the monomer between layers.
This increases the distance between clay layers to some extent before polymerization,
As a result, it is thought that the cohesive force between layers is reduced.
available. Thus, by reducing the cohesion,
For the first time, it is possible to disperse silicate uniformly and molecularly.
It is thought that it is possible. As described above, the copper used in the present invention
Inorganic ions such as ions, hydrogen ions and aluminum ions
A swelling agent consisting of a polyamide monomer molecule
The effect of taking in the clay is very strong,
To increase the cohesion between the layers
The composite material in which the silicate is super-dispersed
A composite material with excellent mechanical properties and heat resistance
it is conceivable that.[0018] The method for producing a composite material according to the present invention comprises
Process-mixing process-polymerization process, composite material with excellent reinforcement
After polymerization, and further heat-melting treatment etc.
Economical and efficient without the need for strength improvement
is there. Further, it can be obtained by the method for producing a composite material of the present invention.
Composite materials are excellent in mechanical strength and heat resistance.
is there. Furthermore, according to the production method of the present invention,
Not only obtains excellent composite materials, but also
Economical and efficient
It can be manufactured in a special way. That is, (1) the present invention
Clay minerals that have adsorbed ions by the lactam compound method
Catalyzes the polymerization of polyamide monomers such as
Ring-opening reaction for the addition of new catalysts and amino acid synthesis
No steps are required. (2) Compounding can be achieved in the heating polymerization process
Therefore, the steps of surface treatment and mixing of the clay mineral can be omitted.
(3) To disperse the silicate layer using a chemical reaction,
The method for crushing and mixing clay minerals can be simplified, and
There is no decrease in the aspect ratio due to oversizing. (4) Clay
Minerals do not alter the polyamide monomer and are preserved.
Because of its excellent storage stability,
And storage and transport in the form of polymer and composite after polymerization
Is possible.[0019] (Embodiment of the invention) The method for producing the composite material of the present invention will be described below.
You. First, the cation exchange capacity is 50-200 meq /
100g clay mineral, copper ion, hydrogen ion, aluminum
Contact with a swelling agent consisting of inorganic cations such as
To form a ionic bond between the two,
Having the property of swelling with monomer at a temperature of
Combine (contact step). This causes the clay mineral to swell
Adsorbs the agent at a temperature above the melting temperature of the monomer.
A complex having the property of swelling with the nomer is obtained.[0020] Here, as the contact method,
After immersing the clay mineral in an aqueous solution containing a swelling agent,
How to remove excess ions by washing soil minerals with water,
Cation exchange resin and clay mineral exchanged with specified swelling agent
A method of exchanging ions by contacting an aqueous suspension of
You.[0021] Clay minerals have a large cation exchange capacity.
Monomer to be reacted with 50-200 meq / 100g
It is a clay mineral with a large contact area with the soil. In particular,
Montmorillonite, Saponite, Hyderite, Nonto
Smoke such as lonite, hectorite, stevensite
Tight clay minerals, vermiculite, halosai
Can be natural or synthetic.
No.[0022] Here, the cation of the clay mineral used in the present invention
Replacement capacity of 50 to 200 meq / 100 g
If the capacity exceeds 200 meq / 100g
In this case, the bonding strength between the layers of the mineral is strong,
This is because it is difficult to obtain a target composite. Ma
The cation exchange capacity of the clay mineral is 50 meq / 10
If it is less than 0 g, it is indispensable in the production method of the present invention.
Swelling comprising organic or inorganic cations
The composite material targeted by the present invention is unable to sufficiently exchange and adsorb the agent.
This is because it becomes difficult to synthesize the ingredients. In addition, this clay mineral
Is a mixer, ball mill, vibratory mill, pin mill,
Pulverize with a mill, beater, etc.
It is preferable to keep the size.[0023] In addition, swelling agents extend between the layers of the clay mineral.
Role and ability to incorporate interlayer polymers into clay minerals
Has the role of givingCopper ion, hydrogen ion
Aluminum ionMore than one kind of inorganic cation such as
A swelling agent is used.[0024] These clay minerals adsorbed by these ions
Is the ring opening weight of a lactam compound such as ε-caprolactam.
It has a catalytic action. Not only that, but of lactam
Produced by ring-opening polymerization or dehydration condensation of amino acids or nylon salts
Capable of incorporating the formed polyamide between clay layers
You. Therefore, use clay minerals that adsorb these ions
By doing so, the hyperdispersed composite according to the present invention is synthesized.
It is.[0025] Initiation of this polymerization reaction or polymerization reaction
In other words, the inorganic cation is (Cu.NH⁺−) And ammo
Nium ion (H₃N⁺Form cationic groups such as-)
Then, an ionic bond is formed with the cationic clay layer.[0026] The inorganic cation used as a swelling agent as described above
Ions act to capture polyamide monomer molecules between layers.
And has a ring-opening polymerization initiating action of the lactam compound,
As the polymerization reaction progresses, the produced polymer is also taken in between the layers.
It also has an effect. Only the above ions allow the polymer to be
Action, that is, the silicate is uniformly molecularly
It is not clear why they have the effect of dispersing in limers
It is not as follows. That is,Copper Io
, Hydrogen ion, aluminum ionInorganic cations such as
In the case of the
The distance between clay layers can be expanded to some extent before polymerization,
It is thought that the cohesive force between the fruit layers can be reduced
Can be Thus, by reducing cohesion,
First, silicate can be uniformly and molecularly dispersed.
It is considered to be.[0027] Next, the composite obtained in the contacting step
And the polyamide monomer are mixed (mixing step). This
Here, the polyamide monomer forms the base of the composite material.
After polymerization, polyamide or polyamide and
It is a raw material that becomes a mixture with the outside polymer, specifically,
6-amino-n-caproic acid, 12-aminododecanoic acid
Amino acid compounds such as hexamethylenediamine
Nylon salt compounds such as phosphates, ε-caprolactam,
Reloractam, caprylactam, α-pyrrolidinone, etc.
Is a lactam compound.[0028] In addition, a mixture of the composite and the polyamide monomer
In this case, the usual mixing method can be adopted.
Is performed by mechanical mixing using an automatic mortar, a vibration mill, or the like.[0029] Next, the mixing obtained in the mixing step
The swelling agent is heated to a predetermined temperature to act as a catalyst.
(Polymerization step). Where the polymerization is mixed
Immediately afterward, the temperature may be raised to a predetermined temperature.
And heat the clay mineral just above the melting point.
-It is more effective to disperse in.[0030] The composite material obtained as described above is directly
It may be used by molding by contact injection molding or heat and pressure molding.
It is mixed with other polymers such as polyamide in advance and
The mixing ratio may be used. In addition, the above polymerization reaction
The molded article may be obtained by advancing in a mold. Polyamide
In the polymerization process of the catalyst, a polymerization catalyst such as phosphoric acid or water is used.
May be added.[0031] In the present invention, the polyamide
Containing resin and uniformly dispersed in the resin in molecular form
A silicate layer having a thickness of 7 to 12 mm.
The distance between the silicate layers is 100 ° or more, and
The silicate layer is ionically bonded to a part of the polyamide polymer chain.
A suitable composite material can be obtained. to this
Mechanical properties such as tensile strength and elastic modulus, and softening temperature
Excellent composite material due to heat resistance such as temperature and high temperature strength
Can be This composite material has strength and heat resistance
If it can be significantly improved compared to conventional nylon
It has a remarkable effect that has not been achieved in the past.[0032] That is, in the method for producing a composite material of the present invention,
The resulting composite material has a polyamide molecular chain with a silicate layer.
Has a structure bridged by ionic bonds with
It is difficult to thermally or mechanically deform
You. Therefore, mechanical properties such as tensile strength and elastic modulus,
Excellent heat resistance such as softening temperature and high temperature strength. Ma
In addition, the layered inorganic substance is uniformly dispersed,
Excellent in qualitative, abrasion resistance, surface lubrication, water permeability and water resistance
I have. Also, the silicate, which is an inorganic layered material, is about 10%.
Dispersed in units of thickness at the molecular level, that is, the molecular length
Disperse the silicate of about 10 分子 in the resin uniformly and molecularly.
ing. Accordingly, in the present invention, a resin containing polyamide is used.
In fats, layered silicates are incorporated at the molecular level,
By dispersing evenly in a separated state for each layer
Thus, the strength of the composite can be improved. Also, silicon
The acid salt layer is strongly bonded to the organic molecular chains. That is,
The silicate layer is ionically bonded to a part of the polyamide polymer chain.
Is seen in conventional inorganic composite materials
No adverse effects such as embrittlement are left. Also, the tree
The distance between the layers of the silicate dispersed in the fat is 100 mm or more.
You. Thus, layered silica is contained in the resin containing polyamide.
Composite material in which salt is dispersed with an interlayer distance of 100 ° or more
Mechanical strength and heat resistance of the composite
Improves strength and resistance better than ordinary nylon
Thermal properties can be obtained.[0033] As described above, the product obtained by the production method of the present invention is obtained.
Composite materials have excellent mechanical strength and heat resistance.
It is considered that the material could be used.[0034] Obtained by the method for producing a composite material of the present invention.
The resin in the composite material is a resin containing polyamide.
With polyamide or polyamide and other polymers
Is a resin comprising a mixture of[0035] Here, polyamide is an acid amide bond
A general term for polymers having (-CONH-), specifically
Nylon 66, nylon 6, nylon 11, and the like.
This resin contains more polyamide resin
The effect of the present invention can be remarkably exhibited as
Even if the content ratio is 10% by weight (wt%), the effect of the present invention
Fruit can be played.[0036] In addition, the silicate layer is a mechanical material
Imparts heat resistance and heat resistance, and has a thickness of 7 to 12
マ グ ネ シ ウ ム From magnesium silicate layer or aluminum silicate layer
It is a layered phyllosilicate mineral formed. These silicic acids
The salt layer is negatively charged due to isomorphous ion substitution or the like. This
Although its characteristics vary depending on the density and distribution of negative charges,
In the present invention, the occupied area of the layer surface per one valence of negative charge is 25.
~ 200ŲThe silicate layer is preferably[0037] The composite material obtained according to the present invention is described above.
Resin containing polyamide, and uniformly molecularly in the resin
And a dispersed silicate layer.[0038] Here, silicate in resin containing polyamide
The content of the layer is 0.5 to 15 with respect to 100 parts by weight of the resin.
It is preferably 0 parts by weight. This means that the content
Less than 0.5 part by weight is sufficient because the silicate layer is too small
This is because a strong reinforcing effect cannot be obtained. In addition, the content
Is more than 150 parts by weight, the resin component is small.
Intermediate compound powder is merely obtained, and this is used as a compact.
Because it is difficult to use. In addition, more suitably
Means that the content of the silicate layer is 100 parts by weight of the resin.
0.5 to 25 parts by weight. Furthermore, optimally, silicate
The content of the layer is 0.5 to 10 with respect to 100 parts by weight of the resin.
Parts by weight. As a result, in the resin containing polyamide
In addition, a silicate layer with a distance of 100 mm or more
And it is possible to obtain a composite material that is sufficiently dispersed in molecular form.
Mechanical properties such as tensile strength and elastic modulus
And excellent heat resistance such as softening temperature and high temperature strength.
A composite material can be obtained. This composite has strength and
And heat resistance are significantly improved compared to conventional nylon.
Has a remarkable effect that has not been achieved before.[0039] This composite material is made of a negatively charged clay mineral
Silicate layer as a structural unit and part of polyamide in resin
Forms an ionic bond with the positively charged group of
The positive charge includes the interaction between the monomer molecule and the inorganic molecule.
The formed cationic group (-NX⁺Group: X is hydrogen
(H), methyl ((CH₃)₃), Copper (Cu), aluminum
Of at least one element such as aluminum (Al).
+3).[0040] That is, the conventional clay / polyamide composite
In the composite obtained by the production method of the coalescence, the clay layer
In the case of a material dispersed with a large interlayer distance as
The tensile strength of the resin as a matrix
Degrees or less (for example, the tensile strength of nylon 6 or less).
This is because, in the first place, in the prior art, clay is contained in polyamide.
When dispersed and hybridized, it is better than the original resin
It is said that mechanical strength such as tensile strength decreases.
The present invention does not rely on this prior art concept,
Mechanical strength and heat resistance of the molded body obtained from the original resin alone
The purpose was to improve the nature,
With the above configuration, mechanical properties such as tensile strength and elastic modulus
And those with excellent heat resistance properties such as softening temperature and high temperature strength
It has been realized. As a result, the present invention provides a mechanical strength
Temperature and heat resistance are significantly improved compared to conventional nylon.
Has an unprecedented effect that can be achieved
Can be[0041] Preferred duplication obtained by the production method of the present invention
The composite material consists of a resin containing polyamide and
And a composite material consisting of a molecularly dispersed silicate layer
So, The silicate layer has a thickness of 7 to 12 mm and the silicate layer
Is greater than 100 ° and the silicate layer is negative
The positive charge of a part of the polyamide in the resin
Forming an ionic bond with the group having
The area per hit is 25-200Å ² And the silicate
The layer is ionically bonded to a part of the polymer chain of the polyamide.
And the content of the silicate layer is based on 100 parts by weight of the resin.
0.5 to 150 parts by weight, Polyamide in the resin
Has a cationic group (-NX) ⁺ X) is hydrogen
(H), methyl ((CH ₃ ) ₃ ), Copper (Cu), aluminum
One or two or more elements of aluminum (Al), Ma
Better mechanical strength and strength than the resin
With excellent mechanical strength and heat resistance
It is characterized by having. [0042] Suitable obtained by the production method of the present invention
Complex materials have a polyamide molecular chain that is ionized with the silicate layer.
Because it has a structure bridged by bonding,
Or it is difficult to deform mechanically. for that reason
In addition, mechanical properties such as tensile strength and elastic modulus, softening temperature and high
Excellent heat resistance such as temperature strength. Also, layered inorganic
Dimensional stability and abrasion resistance due to the uniform distribution of the substance
Excellent in water resistance, surface lubricity, water permeability and water resistance. Also,
The molecular level of silicate, which is an inorganic layered material, is about 10 °.
Dispersion in units of thickness of metal, ie, molecular length is about 10Å
Is uniformly molecularly dispersed in the resin. this
According to the present invention, in the resin containing polyamide,
Separation of silicates at the molecular level, that is, for each crystal unit layer
Of the complex by dispersing it in a uniform state
The degree can be improved. The silicate layer is made of organic
Strongly bound to molecular chains. That is, the silicate layer
Since it is ionically bonded to a part of the polymer chain of lamide,
Embrittlement like that of conventional inorganic composites
No adverse effects are left. Also dispersed in the resin
The distance between the silicate layers is 100 ° or more. like this
And a tree containing polyamide 100% layered silicate in fat
A composite material dispersed with the above interlayer distance
By improving the mechanical strength and heat resistance of the composite,
Excellent strength and heat resistance higher than ordinary nylon
Can be. Here, the silicate layer is mechanically attached to the polymer material.
It imparts properties and heat resistance, and has a thickness of 7 to 1
2% magnesium silicate layer or aluminum silicate layer
It is a layered phyllosilicate mineral formed. And this
These silicate layers are negatively charged due to isomorphous ion substitution, etc.
Has the positive charge of some of the polyamides in the resin
To form an ionic bond with the negatively charged group.
The area of 25 ~ 200Å ² And the silicate layer is
It is formed by ionic bonding with a part of the polyamide polymer chain. Ma
Further, the polyamide in the resin partially contains a cationic group (-
NX ⁺ X is hydrogen (H), methyl ((C
H ₃ ) ₃ ), A type of copper (Cu), aluminum (Al)
Or two or more elements. Also contains polyamide
The content of the silicate layer in the resin is 100 parts by weight of the resin.
0.5 to 150 parts by weight. This means that the content
Less than 0.5 part by weight is sufficient because the silicate layer is too small
This is because a strong reinforcing effect cannot be obtained. In addition, the content
Is more than 150 parts by weight, the resin component is small.
Intermediate compound powder is merely obtained, and this is used as a compact.
Because it is difficult to use. As described above, the present invention
Composite materials have mechanical properties such as tensile strength and elastic modulus
And composite materials with excellent heat resistance such as softening temperature and high temperature strength
It is thought that it was able to be made a fee. That is,
Obtained by the conventional method of manufacturing clay-polyamide composite
The composite has a large interlayer distance, as in the present invention.
Because it is not dispersed,
Or less than the strength of the resin
Below the tensile strength). This is, in the first place, a prior art
Let's disperse clay in polyamide and hybridize
And mechanical strength such as tensile strength is higher than the original resin
It is said to fall. The present invention considers this prior art.
It can be obtained with the original resin alone, not depending on how
The purpose is to improve the mechanical strength and heat resistance of the molded body
With the above configuration, the tensile strength
And mechanical properties such as elastic modulus, softening temperature and high temperature strength
With excellent heat resistance It is. to this
Thus, the present invention provides the mechanical strength and heat resistance of a conventional nail.
Conventional that it can be significantly improved than Ron
It is thought that it can produce a remarkable effect not found in
It is. [0043] Suitable obtained by the production method of the present invention
Complex materials have mechanical properties such as tensile strength and elastic modulus.
And excellent heat resistance such as softening temperature and high temperature strength.
It is a composite material. That is, the composite material has strength and
Heat resistance can be significantly improved compared to conventional nylon
It has excellent characteristics that have never been achieved before. An embodiment of the present invention will be described below. (Example 1) Montmorillonite from Yamagata Prefecture (cation exchange)
Exchange capacity: 100 meq / 100 g) as a swelling agent
A lactam was prepared using the composite shown in Table 1
The compound was polymerized. [0046] [Table 1] First, a swelling agent was added to montmorillonite.
All the inorganic cations shown in Table 1 were adsorbed. This place
If the adsorbed cation is aluminum ion (Al³⁺)of
In such cases, the resin is adsorbed in advance on an ion-exchange resin
The aqueous suspension of montmorillonite in a column packed with
It was adsorbed by flowing. In the case of other cations,
Chloride aqueous solution containing ions to be deposited (concentration 1 normal) 1
After immersing 10 g of montmorillonite in a liter,
By repeating filtration-washing using Funner funnel
went. The ion-exchanged montmorillonite and
Mix ε-caprolactam at a predetermined ratio using a mortar
After that, put it in aluminum container and put it at 80 ° C for 3 hours
Drying and melting of ε-caprolactam
Was. Put the obtained thing in a stainless steel sealed container,
Heat treatment was performed at 250 ° C. for 5 hours to obtain a product. this
Is heated at 2 ° C./min using a DSC (differential scanning calorimeter).
The heat of fusion of the product is measured and the polyamide
Conversion was estimated. Also, the degree of dispersion is determined by X-ray diffraction.
And the distance between the silicate layers was measured. Result obtained
Are shown in Table 1. For comparison, instead of the swelling agent described above,
Sodium ion (Na⁺), Magnesium ion (M
g²⁺), And a surfactant (NH₃ ⁺(CH₂)₁₇
CH₃) Was used in the same manner as in Example 1 except that
A comparison complex was obtained (sample numbers: C1 to C3),
Estimation of conversion rate of metal and measurement of distance between silicate layers
Was. The results obtained are shown in Table 1. The montmorillon treated with aminosilane
The same ratio of lonite (montmorillonite: 10 g)
Ron 6: 100 g) (sample number: C4)
And nylon 6 only (sample number: C5) as above
Molded. Next, the composite materials of Sample Nos. 1 to 5 and
The composites C1 to C5 for comparison are molded by an injection molding machine,
A test piece was obtained. Using this test piece, a tensile test (JI
SK7113) and the heat distortion temperature were measured. That
As a result, the composite material of this example according to the present invention
Material with better mechanical strength and heat resistance than the material
It was confirmed that. That is, the composite material obtained by this embodiment
The material improves the mechanical strength and heat resistance of the composite,
Strength and heat resistance higher than ordinary nylon (Comparative Example: C5)
It can be seen that is obtained. Further, as in Comparative Examples C1 to C3, a swelling agent
Instead of Na⁺And Mg²⁺, NH3⁺(CH₂)
₁₇CH₃In the case of using clay, the clay layer is
Since it is not distributed with a large interlayer distance,
Resin (nylon 6) with tensile strength as matrix
It was confirmed that the strength was not more than. Thus, in the present embodiment, the tensile strength and
Mechanical properties such as elastic modulus and softening temperature and high temperature strength
A composite material with excellent heat resistance can be obtained.
The material has higher mechanical strength and heat resistance than conventional nylon.
It can be seen that the improvement was remarkable.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08G69 / 26 NSC C08G 69/26 NSC C08K 3/34 C08K 3/34 (72) Inventor Shigetoshi Sugiyama No. 41, Nagakute-machi, Yokomichi, Nagakute-cho, Aichi-gun, Japan. Examiner at Toyoda Central Research Laboratory, Inc. Seiji Sakano (56) References JP-A-51-106147 (JP, A) A) JP-A-51-109998 (JP, A) JP-A-57-83551 (JP, A) JP-A-7-309942 (JP, A)

Claims (1)

(57) [the claims] 1. Cation exchange capacity is 50-200 meq / 10
0 g of a clay mineral is brought into contact with a swelling agent comprising one or more inorganic cations of copper ions, hydrogen ions, and aluminum ions to form an ionic bond between the two and swell with the monomer at a temperature higher than the melting temperature of the monomer. consists of a contacting step to complex with the nature, the step of mixing the complex with polyamide monomers, a polymerization step of polymerizing the mixture to the original catalysis of by heating pressurizing the swelling agent, which Is a composite material comprising a polyamide-containing resin and a silicate layer uniformly and molecularly dispersed in the resin, wherein the silicate layer has a thickness of 7 to 12 mm and an interlayer between the silicate layers. distance is not less 100Å or more, yet該珪salt layer has a negative charge, it forms a group and ionic bond with a positive charge with a portion of the polyamides, the negative charge monovalent per area 25 ~ 20 A Å ^2, and the silicate layer is then partially ionic bonds of the polymer chain of the polyamide, the content of silicate layers with respect to 100 parts by weight of the resin 0.5-1
A method for producing a composite material, comprising obtaining a composite material having excellent mechanical strength and heat resistance of 50 parts by weight. 2. Swelling agent is aluminum ion, hydrogen ion,
The method for producing a composite material according to claim 1 , wherein the composite material is one or a mixture of two or more types of copper ions. 3. Polyamide monomers, method of producing a composite material according to claim 1, wherein the lactam compound. 4. Polyamide monomers, method of producing a composite material according to claim 1, wherein the amino acids. 5. Polyamide monomers, method of producing a composite material according to claim 1, wherein the nylon salt. 6. The content of the silicate layer in the composite material, method for producing a composite material according to claim 1, characterized in that 0.5 to 25 parts by weight per 100 parts by weight of the resin. 7. The content of the silicate layer in the composite material, method of manufacturing a composite material according to claim 1, wherein the 0.5 to 10 parts by weight per 100 parts by weight of the resin.