阅读说明：本技术 一种抗翘曲pa6复合材料及其制备工艺及塑料件 (Anti-warping PA6 composite material, preparation process thereof and plastic part ) 是由 陈奕欣 于 2021-09-28 设计创作，主要内容包括：本申请涉及复合材料领域,具体公开了一种抗翘曲PA6复合材料及其制备工艺及塑料件包括以下重量百分比的组分：PA6 66-70%、改性实心玻璃微珠18-22%、玻璃纤维8-13%、有机硅1-3%；其制备方法为：(1)初混；(2)复混；(3)制备中间料；(4)冷却、切粒、筛选。本申请的产品可用于塑料件的制造,其具有抗翘曲性强的优点。(The application relates to the field of composite materials, and particularly discloses an anti-warping PA6 composite material, a preparation process thereof and a plastic piece, wherein the anti-warping PA6 composite material comprises the following components in percentage by weight: PA 666-70%, modified solid glass bead 18-22%, glass fiber 8-13%, organosilicon 1-3%; the preparation method comprises the following steps: (1) primary mixing; (2) compounding; (3) preparing an intermediate material; (4) cooling, granulating and screening. The product of this application can be used for the manufacturing of working of plastics, and it has the strong advantage of anti warpage nature.)

1. A warp-resistant PA6 composite material, characterized by: comprises the following components in percentage by weight: PA 666-70%, modified solid glass bead 18-22%, glass fiber 8-13% and organic silicon 1-3%.

2. The warp-resistant PA6 composite material according to claim 1, wherein: the preparation method of the modified solid glass bead comprises the following steps: stirring and mixing the solid glass beads and the silane coupling agent compound, drying for 2-3h, and drying at the temperature of 155-165 ℃ to prepare modified solid glass beads; the mass fraction of the silane coupling agent compound is 0.1-1%.

3. The warp-resistant PA6 composite material according to claim 2, wherein: the silane coupling agent compound comprises the following components in percentage by weight: 34-40% of silane coupling agent, 0.1-1% of nonionic surfactant and 60-66% of water.

4. A warp-resistant PA6 composite material according to claim 3, wherein: the silane coupling agent is one or a mixture of KH550 and KH 570.

5. The warp-resistant PA6 composite material according to claim 4, wherein: the nonionic surfactant is fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether or a mixture of the fatty alcohol polyoxyethylene ether and the alkylphenol polyoxyethylene ether.

6. The warp-resistant PA6 composite material according to claim 1, wherein: the weight ratio of the modified solid glass beads to the glass fiber is 20 (8-13).

7. The warp-resistant PA6 composite material according to claim 6, wherein: the weight ratio of the modified solid glass beads to the glass fiber is 2: 1.

8. The warp-resistant PA6 composite material according to claim 1, wherein: the organic silicon is polydimethylsiloxane.

9. A process for preparing a warp-resistant PA6 composite material according to any one of claims 1 to 6, wherein: the method comprises the following steps:

(1) primary mixing: weighing the modified glass beads and the organic silicon according to the weight ratio, and uniformly mixing to obtain a primary mixture;

(2) compounding and mixing: adding PA6 into the primary mixture obtained in the step (1) according to the weight ratio, uniformly mixing, and adding into a high-speed mixer for blending to obtain a compound mixture;

(3) preparing an intermediate material: adding the mixture obtained in the step (1) into an extruder, weighing glass fibers according to the weight ratio, adding the glass fibers from a side feeding port of the extruder, and extruding an intermediate material by the extruder;

(4) cooling, granulating and screening: and (4) cooling, granulating and screening the intermediate material in the step (3) to obtain the anti-warping PA6 composite material.

10. A plastic article, comprising: made of the warp-resistant PA6 composite material according to any of the preceding claims 1-6.

Technical Field

The invention relates to the field of composite materials, in particular to an anti-warping PA6 composite material, a preparation process thereof and a plastic part.

Background

Polyamide (PA) is commonly called nylon, is a general name of thermoplastic resin containing repeated amide groups- (NHCO) -on a molecular main chain, comprises PA6, PA66, PA12 and the like, and has large yield and wide application. Among them, PA6 has better rebound resilience, fatigue resistance and thermal stability, so it is widely used to prepare plastic parts for automobiles, especially thin-walled plastic parts.

The mechanical strength of PA6 can be effectively improved by adding a proper amount of glass fiber and/or carbon fiber into PA6, but the plasticity of the PA6 composite fiber obtained by modifying the glass fiber and/or the carbon fiber is poor due to poor fluidity of the glass fiber and the carbon fiber. When the modified PA6 composite material is used for preparing a thin-wall plastic part, the thin-wall plastic part is easy to warp and deform, so that the yield of the thin-wall plastic part is low.

Disclosure of Invention

In order to improve the warping resistance of thin-wall plastic parts, the application provides a warping-resistant PA6 composite material, a preparation process thereof and a plastic part.

In a first aspect, the present application provides a warp-resistant PA6 composite material, which adopts the following technical scheme:

a warp-resistant PA6 composite material comprises the following components in percentage by weight: PA 666-70%, modified solid glass bead 18-22%, glass fiber 8-13% and organic silicon 1-3%.

By adding the glass fiber, the mutual movement among PA6 high polymer chains is limited, so that the shrinkage rate of the anti-warping PA6 composite material is obviously reduced, the rigidity is greatly improved, and the impact resistance and the tensile strength of the anti-warping PA6 composite material are enhanced.

Because the glass fiber has anisotropy, after the glass fiber is added into the PA6 composite material, different shrinkages can be generated in different directions, the modified solid glass beads are added, and the modified solid glass beads are uniformly dispersed in the anti-warping PA6 composite material, so that the viscosity of the interior of the anti-warping PA6 composite material is reduced, the anti-warping PA6 composite material has uniform shrinkages in all directions, and the quality of the plastic part manufactured by the method is more controllable. In addition, because the modified solid glass beads are solid and small particles, the modified solid glass beads can be uniformly dispersed in the PA6 composite material by adding the modified solid glass beads, so that the wear resistance of the plastic part prepared from the modified solid glass beads is enhanced.

According to the application, the organosilicon is added, so that the flowability in the PA6 mixture is increased, the demolding performance of the anti-warping PA6 composite material is enhanced, the melt fracture of the anti-warping PA6 composite material is eliminated, and the impact strength of the anti-warping PA6 composite material is obviously improved.

Preferably, the preparation method of the modified solid glass bead comprises the following steps: stirring and mixing the solid glass beads and the silane coupling agent compound, drying for 2-3h, and drying at the temperature of 155-165 ℃ to prepare modified solid glass beads; the mass fraction of the silane coupling agent compound is 0.1-1%.

According to the application, the silane coupling agent compound is added, the solid glass beads are fully infiltrated by the silane coupling agent compound, so that the solid glass beads can be dispersed more uniformly in the anti-warping PA6 composite material, and a plastic part prepared from the solid glass beads has better mechanical performance.

Preferably, the silane coupling agent compound comprises the following components in percentage by weight: 34-40% of silane coupling agent, 0.1-1% of nonionic surfactant and 60-66% of water.

As the silane coupling agent has higher optimization performance on the solid glass beads in a wet state, the solid glass beads are treated by adding the silane coupling agent in the wet state, so that alkoxy is hydrolyzed by the silane coupling agent to generate silanol, and the silanol and Si-OH on the surfaces of the solid glass beads are subjected to condensation reaction to form chemical bonds, and the adhesive force of the solid glass beads in PA6 can be obviously enhanced.

In addition, the nonionic surfactant has better solubility in water and organic matters, so that the silane coupling agent is uniformly and stably dispersed in the water by adding the nonionic surfactant, the surfaces of the solid glass beads are fully contacted with the silane coupling agent compound, and the dispersibility of the solid glass beads in the anti-warping PA6 composite material can be enhanced.

Preferably, the silane coupling agent is one or a mixture of two of KH550 and KH 570.

The modified solid glass microspheres can have stronger dispersity in the PA6 mixture by adding one or a mixture of KH550 and KH570, so that plastic parts prepared from the modified solid glass microspheres have higher tensile strength and impact failure resistance.

Preferably, the nonionic surfactant is one or a mixture of two of fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether.

Because the fatty alcohol-polyoxyethylene ether and the alkylphenol polyoxyethylene ether are common dispersing agents, the silane coupling agent can be fully dispersed to form a wet silane coupling agent by adding one or a mixture of the fatty alcohol-polyoxyethylene ether and the alkylphenol polyoxyethylene ether, so that the dispersibility of the modified solid glass beads is improved, and the tensile strength and the impact and damage resistance of the plastic part prepared from the modified solid glass beads are enhanced.

Preferably, the weight ratio of the modified solid glass beads to the glass fiber is 20 (8-13).

According to the application, the modified solid glass beads and the glass fibers in the range are added and uniformly mixed in the anti-warping PA6 composite material, so that the shrinkage rates of the anti-warping PA6 composite material in all directions are closer, and all parts of the manufactured product shrink more uniformly and have stronger anti-warping property.

Preferably, the weight ratio of the modified solid glass beads to the glass fiber is 2: 1.

According to the application, the modified solid glass beads and the glass fibers in the range are added and uniformly mixed in the anti-warping PA6 composite material, so that the shrinkage rate of the anti-warping PA6 composite material in all directions is more uniform, and the plastic part prepared from the anti-warping PA6 composite material has better anti-warping performance.

Preferably, the silicone is polydimethylsiloxane.

Because of the non-adhesiveness of polydimethylsiloxane, PA6 and the like, the warp-resistant PA6 composite material can be more conveniently demoulded by adding the polydimethylsiloxane, and a plastic part prepared from the warp-resistant PA6 composite material has a clean and smooth surface and clear texture. In addition, polydimethylsiloxane has excellent thermal oxidation stability and small change of viscosity and acid value, and the performance of the plastic part prepared by adding polydimethylsiloxane can be more stable.

In a second aspect, the application provides a preparation process of a warp-resistant PA6 composite material, which adopts the following technical scheme: a preparation process of a warp-resistant PA6 composite material comprises the following steps:

(1) primary mixing: weighing the modified solid glass microspheres according to the weight ratio, and uniformly mixing the modified solid glass microspheres and the organic silicon to obtain a primary mixture;

(2) compounding and mixing: adding PA6 into the primary mixture obtained in the step (1) according to the weight ratio, uniformly mixing, and adding into a high-speed mixer for blending to obtain a compound mixture;

(3) preparing an intermediate material: adding the mixture obtained in the step (1) into an extruder, weighing glass fibers according to the weight ratio, adding the glass fibers from a side feeding port of the extruder, and extruding an intermediate material by the extruder;

(4) cooling, granulating and screening: and (4) cooling, granulating and screening the intermediate material in the step (3) to obtain the anti-warping PA6 composite material.

After the modified solid glass beads and the organic silicon are uniformly mixed, the organic silicon is uniformly attached to the surfaces of the modified solid glass beads, so that the modified solid glass beads are uniformly dispersed in PA6, and the glass fibers are added after blending by a high-speed mixer, so that the PA6 mixture is uniformly shrunk in all directions, and the warping resistance of the warping-resistant PA6 composite material is improved.

In a third aspect, the present application provides a plastic part, which adopts the following technical solutions:

a plastic part made of the above warp resistant PA6 composite material.

The thin-shell plastic part made of the anti-warping PA6 composite material is not easy to warp and has high qualification rate.

In summary, the present application has the following beneficial effects:

1. by arranging the modified solid glass beads to match with the glass fibers, the impact resistance and tensile strength of the glass fiber reinforced anti-warping PA6 composite material are improved, and the shrinkage rate of the PA6 anti-warping composite material in each direction is coordinated by the modified solid glass beads, so that the warping resistance, tensile strength and impact resistance of the anti-warping PA6 composite material are improved; by adding the organic silicon into the anti-warping PA6 composite material, the modified solid glass beads and the glass fibers are conveniently and uniformly dispersed in the anti-warping PA6 composite material, so that the anti-warping PA6 composite material has stronger mechanical property and anti-warping property.

Detailed Description

The present application will be described in further detail with reference to examples.

Raw materials

The raw material components of the invention are shown in the table 1:

TABLE 1 sources of the raw material components

Examples

Examples 1-7 were prepared in the same manner, except that the component materials were varied in weight as shown in Table 2.

The preparation method of the modified solid glass bead comprises the following steps:

s1: weighing 33kg of KH550, 58kg of water and 0.1kg of fatty alcohol-polyoxyethylene ether according to the weight percentage, and uniformly mixing to obtain a silane coupling agent compound;

s2: 200kg of solid glass microspheres and 2kg of silane coupling agent compound are placed in a stirring treatment device according to the weight percentage to be stirred and mixed to obtain a primary product, the pH value of the solution is controlled to be 3.5-5.5 in the stirring process,

s3: filtering the primary product, drying for 2-3h, and drying at 155-165 ℃ for 30-60min to obtain the modified solid glass microspheres.

A preparation process of a warp-resistant composite material comprises the following steps:

(1) primary mixing: weighing 22kg of modified solid glass microspheres and 1kg of organic silicon according to the weight percentage, and uniformly mixing to obtain a primary mixture;

(2) compounding and mixing: adding 69kg of PA6 into the primary mixture according to the weight percentage, uniformly mixing, adding into a high-speed mixer, and blending for 5-15min to obtain a compound mixture;

(3) preparing an intermediate material: adding the mixture into an extruder, weighing 8kg of glass fiber according to the weight ratio, adding the glass fiber from a side feeding port of the extruder, and extruding an intermediate material by the extruder; the process parameters of the extruder are as follows: the temperature of the first zone is 220-245 ℃, the temperature of the second zone is 220-245 ℃, the temperature of the third zone is 220-245 ℃, the temperature of the fourth zone is 220-245 ℃, the temperature of the fifth zone is 220-245 ℃, the temperature of the sixth zone is 220-245 ℃, the temperature of the seventh zone is 215-240 ℃, the temperature of the eighth zone is 215-240 ℃, the temperature of the ninth zone is 215-240 ℃, the pressure is 20-23MPa, and the rotation speed of the screw is 360-430 r/min;

(4) cooling, granulating and screening: and cooling, granulating and screening the intermediate material to obtain the anti-warping PA6 composite material.

TABLE 2 materials and their weights in examples 1-7

Example 8

The difference from example 2 was that the amount of KH550 added in S1 was 37kg, and the amount of water added was 63 kg.

Example 9

The difference from example 2 was that the amount of KH550 added in S1 was 40kg, and the amount of water added was 60 kg.

Example 10

The difference from the example 8 is that the addition amount of KH550 in S1 is 36.815kg, the addition amount of water is 61.69kg, and the addition amount of fatty alcohol-polyoxyethylene ether is 0.5 kg.

Example 11

The difference from example 8 is that the amount of KH550 added in S1 was 36.63kg, the amount of water added was 61.38kg, and the amount of fatty alcohol-polyoxyethylene ether added was 1 kg.

Example 12

The difference from example 8 is that no fatty alcohol-polyoxyethylene ether is added in S1.

Example 13

The difference from example 8 is that the amount of KH550 added in S1 is 36.26kg, the amount of water added is 60.76kg, and the amount of fatty alcohol-polyoxyethylene ether added is 2 kg.

Example 14

The difference from example 11 was that the amount of the silane coupling agent complex added in S2 was 0.2 kg.

Example 15

The difference from example 11 was that the amount of the silane coupling agent complex added in S2 was 1 kg.

Example 16

The difference from example 11 is that no silane coupling agent complex was added in S2.

Example 17

The difference from example 11 was that the amount of the silane coupling agent complex added in S2 was 4 kg.

Example 18

The difference from example 11 is that fatty alcohol polyoxyethylene ether was replaced with glycerin fatty acid ester available from Shanghai Michelin Biotech, Ltd.

Example 19

The difference from example 11 was that the polydimethylsiloxane was replaced with silicone powder from Jeccard chemical Co., Ltd, Hangzhou.

Comparative example

Comparative example 1

The difference from example 14 was that the amount of modified solid glass beads added was 8 kg.

Comparative example 2

The difference from example 14 was that the amount of modified solid glass beads added was 24 kg.

Comparative example 3

The difference from example 14 was that the amount of glass fiber added was 7.4 kg.

Comparative example 4

The difference from example 14 was that the amount of glass fiber added was 17.9 kg.

Comparative example 5

The difference from example 14 was that the modified solid glass beads were replaced with hollow glass beads from 3M company.

Comparative example 6

30% glass fiber reinforced PA6 from BASF corporation.

Performance test

The warp-resistant composite materials prepared in examples 1 to 19 and comparative examples 1 to 6 were each prepared by randomly taking 3 pieces of 30cm × 30cm × 2.5mm in size, one for each 3 pieces, and the following performance test experiments were performed on each set of samples, and the three monitored data of each set were averaged.

First, tensile strength test

Each sample was formed into a pattern of a predetermined size by referring to the method for measuring the tensile strength of A6 composite in ASTM D638-03, method for measuring tensile Properties of plastics, and the tensile yield strength (50mm/min) (MPa) and tensile modulus of elasticity (MPa) of the patterns in examples and comparative examples were calculated by examining the patterns and recording the data.

Second, bending Strength test

The flexural strength (2mm/min) and flexural modulus (MPa) of the specimens in examples and comparative examples were calculated by taking samples of each specimen in a predetermined size and testing the samples by reference to the flexural strength test method for PA6 composite in ASTM D790-03 Standard test method for flexural Properties of unreinforced and reinforced plastics and Electrical insulation materials, and recording the data.

Third, notched impact Strength test

Referring to the method for testing notched impact strength of PA6 composite material in ASTM D256-06 Standard test method for testing cantilever pendulum impact resistance of plastics, each sample was prepared in a pattern of a prescribed size, the pattern was examined and data was recorded to calculate the notched impact strength (23 ℃ C.) (KJ/m) of IZOD in the samples of examples and comparative examples²)。

Fourth, warping condition

The warpage-resistant composite materials prepared in examples 1 to 19 and comparative examples 1 to 6 were randomly prepared into 3 pieces of 30cm × 30cm × 2mm size, respectively, and each of the 3 pieces was measured for warpage amount (mm) for each set of samples, and the average value of three monitored data for each set was obtained.

And (3) detection results: the results of the tests on the samples obtained in examples 1 to 19 and comparative examples 1 to 6 are shown in Table 3.

Table 3 type performance test results table

Since the content of PA6 used in this application is very high compared to the content of added silicone, and the effect of other components in the raw materials is not affected after the silicone is added, in examples 4 and 5, PA6 is used to supplement the amount of added silicone.

It can be seen by combining examples 1-19 and comparative example 6 with Table 3 that none of the tensile yield strength, tensile elastic modulus, flexural strength and IZOD notched impact strength of the samples made with the raw materials within the preferred ranges of the present application are significantly lower than those of the commercially available 30% glass fiber reinforced PA6 composite material, and the warpage amount of the samples made with the raw materials within the preferred ranges of the present application is less than 0.3mm, i.e., the samples made with the raw materials within the preferred ranges of the present application significantly enhance the warpage resistance of the product without unduly decreasing the tensile strength, flexural strength and impact strength of the product.

As can be seen by combining example 14 with comparative examples 1 and 2 and table 3, the tensile yield strength, tensile elastic modulus and flexural strength of the samples made with the solid glass beads within the preferred ranges of the present application are higher, the tensile yield strength, tensile elastic modulus and flexural strength of the samples made with too few glass beads are lower, and the IZOD notched impact strength of the samples made with too many glass beads is slightly lower, i.e., the samples made with the glass beads within the preferred ranges of the present application have better tensile strength, flexural strength and impact strength.

It can be seen by combining example 14 with comparative examples 3 and 4 and by combining table 3 that the tensile yield strength and IZOD notched impact strength of the samples made with glass fibers within the preferred ranges of the present application are significantly higher, the tensile yield strength of the samples made with too few glass fibers is slightly lower and the IZOD notched impact strength is significantly lower, the tensile yield strength, tensile elastic modulus and flexural strength of the samples made with too many glass fibers are significantly lower, i.e., the tensile yield strength and flexural strength of the samples made with glass fibers within the preferred ranges of the present application are both better than those of the samples made with too many or too few glass fibers and the impact strength of the samples made with too few glass fibers is lower.

Combining example 14 and comparative example 5 with table 3, it can be seen that the samples made with the modified solid glass beads had significantly higher IZOD notched impact strength and smaller warpage, and the samples made with the hollow glass beads had significantly lower IZOD notched impact strength and warpage of greater than 0.3mm, i.e., the samples made with the modified solid glass beads had better notched impact strength and warpage resistance.

As can be seen by combining examples 1-3 with Table 3, the samples made with glass beads and glass fibers added in the preferred ranges of example 2 have higher tensile yield strength, tensile elastic modulus and bending strength, and the samples made with glass beads and glass fibers added in the preferred ranges of the present application have similar IZOD notched impact strength; that is, the samples made with glass beads and glass fibers in the preferred ranges of the present application had similar impact strength, but the samples made with glass beads and glass fibers in the preferred ranges of example 2 had higher tensile strength and bending strength.

It can be seen from the combination of examples 2, 4 and 5 and table 3 that the samples made by adding the silicone in the preferred range of the present application have higher tensile yield strength, tensile elastic modulus and bending strength, while the samples made by adding the silicone in the preferred range of example 2 have similar tensile yield strength, tensile elastic modulus, bending strength and slightly lower IZOD notched impact strength, i.e. the samples made by using the glass beads and the glass fibers in the preferred range of the present application have similar tensile strength and bending strength, and the samples made by adding the silicone in the preferred range of example 2 have higher impact strength.

As can be seen by combining examples 2, 6 and 7 with Table 3, the samples made with the addition of PA6 in the preferred range of the present application had similar tensile yield strength, tensile elastic modulus, flexural strength, flexural modulus and IZOD notched impact strength, i.e., the samples made with PA6 in the preferred range of the present application had similar tensile strength, flexural strength and impact strength.

It can be seen from the combination of examples 2, 8 and 9 and Table 3 that the samples prepared by adding the silane coupling agent compound in the preferred range have similar tensile yield strength, tensile elastic modulus, bending strength, bending modulus and IZOD notched impact strength, i.e., the products prepared by using the silane coupling agent compound in the preferred range have similar tensile strength, bending strength and impact strength.

As can be seen by combining examples 2, 10-13 with Table 3, the samples made with the nonionic surfactant concentrations of example 11 had higher IZOD notched impact strengths, and the samples made with the nonionic surfactants in the preferred ranges of the present application had similar tensile yield strengths, tensile elastic moduli, flexural strengths and flexural moduli, i.e., similar tensile strengths and flexural strengths were obtained with the concentrations of the nonionic surfactants in the preferred ranges of the present application, but the impact strengths of the products made with the nonionic surfactant concentrations of example 11 were higher.

As can be seen by combining examples 11, 14-17 with Table 3, the samples made with the silane coupling agent composite concentrations of example 11 had higher IZOD notched impact strengths and the samples made with the nonionic surfactants added within the preferred ranges of the present application had similar tensile yield strengths, tensile elastic moduli, flexural strengths and flexural moduli, i.e., similar tensile strengths and flexural strengths with concentrations within the preferred ranges of the present application, but the products made with the nonionic surfactant addition concentrations of example 11 had higher impact strengths.

As can be seen by combining examples 11 and 18 with Table 3, the samples made with the nonionic surfactant of example 11 had higher tensile yield strength, tensile elastic modulus and IZOD notched impact strength, and the nonionic surfactant in the preferred range of the application had similar flexural strength and flexural modulus, i.e., the products made with the nonionic surfactant of example 11 had better tensile strength and impact strength tests.

It can be seen from a combination of examples 11 and 19 and from Table 3 that the samples made with the silicone of example 11 have similar tensile yield strength, tensile elastic modulus, flexural strength, flexural modulus and IZOD notched impact strength, i.e., the silicone with the preferred ranges of this application has similar tensile strength, flexural strength and impact strength.

It can be seen from the combination of example 14 and comparative examples 1 to 4 and table 3 that the samples made of the modified solid glass beads and the glass fibers in the preferred range of the present application have a low warpage amount, and the samples made of the modified solid glass beads and the glass fibers added with too much or too little amount of the modified solid glass beads and the glass fibers have warpage amounts exceeding 0.3mm, i.e., the products made of the modified solid glass beads and the glass fibers in the preferred range of the present application have strong warpage resistance.

In summary, in the example having the tensile strength, the bending strength, the impact strength and the low warpage amount not lower than those of the samples made of the raw materials without using the raw materials within the range of the present application, the warpage amount of example 11 is the lowest, that is, example 11 has the strongest warpage resistance without lowering the tensile strength, the bending strength and the impact strength.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.